MASTER 

NEGATIVE 
NO.  94-8221 2- 12 


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Author: 


U.S.  Dept.  of  Commerce. 


Title: 


Dyestuffs  for  American 
textile  and  other  industries 

Place: 

Washington, 

Date: 

1915 


qc|-82ziz-i 


COLUMBIA  UNIVERSITY  LIBRARIES 
PRESERVATION  DIVISION 

BIBLIOGRAPHIC  MICROFORM  TARGET 


MASTER   NEGATIVE  * 


ORIGINAL  MATERIAL  AS  FILMED  •    EXISTING  BIBLIOGRAPHIC  RECORD 


RESTRICTIONS  ON  USE: 


U.S.    Dept,  of  commerce,  '  . 

...  Dyestuffs  for  American  textile  and  other  industries,  by 
Thomas  H.  Norton,  commercial  agent  of  the  Department  of 
commerce.    Washington,  Govt,  print,  off.,  1915. 

67  p.    diagrs.     25". 

At  head  of  title:  Department  of  commerce.  Bureau  of  foreign  and 
domestic  commerce.    B.  B.  Pratt,  chief.    Special  agents  series — no.  96. 


1.  Dyes  and  dyeing.    2.  Textile  Industry  and  fabrics — V.  S.         I.  Nor- 
ton, Thomas  Herbert,  1851-  .      n.  Title.  — 

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DEPARTMENT   OF    COMMERCE 

BUREAU  OF  FOREIGN  AND  DOMESTIC  COMMERCE 
E.  E.  PRATT,  Chief 


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SPECIAL  AGENTS  SERIES-No.  06 


DYESTUFFS  FOR  AMERICAN  TEXTILE 
AND  OTHER  INDUSTRIES 


BY 


tHTOMAS  H.  NORTON 

CoaimsrcUl  Agent  of  the  Deptnment  of  Commerct 


WASHINGTON 

GOVERNMENT  PRINTING  OFFICi 

1915 


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DEPARTMENT    OF    COMMERCE 

BUREAU  OF  FOREIGN  AND  DOMESTIC  COMMERCE 
E.  E.  PRATT,  Chief 


SPECIAL  AGENTS  SERIES— No.  96 


DYESTUFFS  FOR  AMERICAN  TEXTILE 
AND  OTHER  INDUSTRIES 


BY 


THOMAS  H.  NORTON 

Commercial  Agent  of  the  Department  of  Commerce 


WASHINGTON 
GOVERNAlE^^Jf  ^PINT\NG  OFFICF. 
•    19J5 


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ADDITIONAL  COPIES 

Of  THIS  PUBUCATION  MAT  BE  PROCUKED  FROM 

THE  SX7PERINTENDENT  OF  DOCUMENTS 

GOVERNMENT  PRINTINO  OFFICE 

WASHINGTON,  D.  C. 

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CONTENTS. 


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5 
7 
12 
12 
12 
14 
15 
15 


Letter  of  submittal ^*^®. 

Introduction 

Dyestuff  situation  in  the  United  States '..*... 

Dyestuffs  used  in  the  United  States *  *  * 

Natural  organic  dyes • 

Importation  of  natural  organic  dyes 

Mineral  dyes 

Artificial  organic  dyes 

Domestic  manufacture  of  artificial  dyestuffs i6 

Foreign  sources  of  artificial  dyestuffs 17 

Economic  effects  of  dependence  upon  a  single  foreign  source ^  *  * .  17 

Increased  cost  of  coal-tar  dyes ,« 

^           Outlook  for  the  immediate  future *''  " jg 

Alternatives  in  case  of  a  dyestuff  famine jg 

Outline  of  the  coal-tar  chemical  industry 20 

Coal-tar  dye  industry  in  the  United  States .'.......  2I 

Slow  development  of  the  American  industry /  21 

American  supply  of  raw  materials 

Coal  tar  from  gas  works 

Coal  tar  and  benzol  from  coke  works 

Present  production  of  crude  tar  products ! ." ! .  26 

Price  movement  of  American  coal-tar  crudes 28 

Position  of  the  American  tar  distiller 

Supply  of  general  chemicals  required 

The  German  coal-tar  dyestuff  industry 

Trade  in  crudes  and  intermediates 

Causes  of  Germany's  supremacy Xo 

Research  the  chief  cause 34 

German  industry,  capital,  dividends,  etc * "  * "  *  34 

Geography  of  the  German  industry 35 

Relations  between  companies 05 

Equipment  of  plants 07 

Wages  in  the  German  factories 37 

Processes  of  manufacture «« 

Uniformity  of  product ^ 

Typical  phases ^ 

Illustrative  outlines 4, 

Alizarin,  naphthol  yellow,  magenta 4^ 

Hydroquinone  and  synthetic  indigo \  42 

The  ketone  dyes ^ 

Benzidine  dyes ^^ 

Tolidine  and  allied  dyes '   40 

Patents  in  the  German  industry 40 

American  attitude  toward  the  German  industry 51 

Producers  of  coal-tar  crudes 59 

Manufacturers  of  heavy  chemicals *  52 

Manufacturers  of  artificial  dyestuffs 52 

Consumers  of  artificial  dyestuffs 53 

Economists ^4 

American  Chemical  Society,  New  York  section *  54 

Establishment  of  an  American  industry 55 

The  problem  in  England  and  France Kti 

Summary *'-*-".'."/-'-"..'..".*.*  .'.".V.V.*..'.  57 


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LETTER  OF  SUBMITTAL. 


Department  of  Commerce, 
Bureau  of  Foreign  and  Domestic  Commerce, 

Washington,  March  20 j  1915. 
Sir:  There  is  submitted  herewith  a  report  by  Commercial  Agent 
Thomas  H.  Norton  on  dyes  tuffs  for  American  textile  and  other 
industries.  This  report  was  called  for  by  a  resolution  of  the  Senate, 
under  date  of  January  26,  1915.  It  presents  fully  the  nature  of  the 
dyestuffs  used  by  American  industries  and  the  sources  of  supply, 
showing  the  limited  extent  of  the  domestic  manufacture  and  the 
general  dependence  upon  foreign-made  dyes.  The  predominance  of 
Germany  in  this  field  is  shown,  and  the  reasons  for  this  situation  are 
detailed.  AH  factors  connected  with  the  creation  of  a  self-contained, 
independent,  American  coal-tar  chemical  industry  are  given  in  full, 
and  the  problems  involved  by  a  threatened  cessation  of  the  present 
foreign  supply  are  considered. 

Respectfully, 

E.  E.  Pratt, 
Chief  of  Bureau. 
To  Hon.  William  C.  Redfield, 

Secretary  of  Commerce, 

5 


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DYESTUFFS  FOR  AMERICAN  TEXTILE  AND  OTHER 

INDUSTRIES. 


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INTRODUCTION. 

Under  date  of  January  26,  1915,  the  Senate  of  the  United  States 
passed  the  following  resolution: 

Resolved,  That  the  Secretary  of  Commerce  be,  and  he  is  hereby,  directed  to  inform 
the  Senate  as  fully  aa  possible  as  to  the  facts  relating  to  the  supply  of  dyestufts  for 
American  textile  and  other  industries,  the  sources  of  such  supply,  the  extent  and 
nature  of  the  supply,  the  movement  of  prices,  the  available  materials  for  the  manu- 
facture of  such  supplies  in  this  country,  the  possibilities,  if  any,  as  to  the  stoppage  of 
such  supply  by  reason  of  the  existing  European  war,  and  any  and  all  such  other  facts 
as  will  bring  the  existing  conditions  in  the  aniline  color  industry  fully  to  the  knowledge 
of  the  Senate. 

In  response  to  this  resolution,  the  Secretary  of  Commerce  com- 
municated to  the  Senate,  under  date  of  February  20,  1915,  the  fol- 
lowing preliminary  report,  which  summarizes  the  main  facts  and 
outlines  the  scope  of  the  full  report  as  here  given. 

PRELIMINARY  REPORT. 

Numerous  American  industries  are  closely  dependent  upon  the  use 
of  dyestuffs.  To  the  great  textile  branches  they  are  almost  as  essen- 
tial as  their  supplies  of  vegetable  or  animal  fibers.  The  same  con- 
dition exists  in  the  paint,  varnish,  and  ink  trades,  the  paper  indus- 
try, the  feather  and  leather  trades,  and  a  group  of  minor  industries. 
Dependent  upon  the  products  of  these  industries  are  a  host  of  other 
branches,  all  users  of  textiles.  The  old-time  natural  dyestuffs, 
such  as  indigo,  madder,  cochineal,  orchil,  fustic,  and  a  score  more, 
have  no  longer  an  extended  use,  with  the  exception  of  logwood, 
which  still  plays  a  valued  auxiUary  role.  The  same  is  the  case  with 
mineral  colors,  with  some  inconsiderable  exceptions,  such  as  Prus- 
sian blue  in  silks  and  iron  buff  in  khaki. 

Artificial  dyestuffs,  derived  from  coal-tar  products,  have  displaced 
nearly  all  rivals,  combining  quahties  of  fastness,  ease  of  appUcation, 
briUiancy,  variety  of  shades,  etc.,  utterly  unknown  to  the  former 
generation  of  dyers. 

EFFECT  OF  WAR  ON  DYESTUFF  CONSUMERS. 

The  American  consumption  of  artificial  dyestuffs  has  attained  an 
annual  value  of  $15,000,000,  and  grows  steadily. 

It  is  supphed  partly  by  a.  domestic  production  valued  at  about 
$3,000,000.  This  apparent  domestic  production  is  based  chiefly  upon 
the  use  of  foreign  materials — half-made  or  nearly  completed  color 
compounds.  But  a  small  portion  is  made  from  American  crude  coal- 
tar  compoimds. 


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8 


DYESTUPFS  FOR  AMERICAN  INDUSTRIES. 


The  great  bulk  of  the  artificial  dyestuff  supply  comes  from  Europe. 

I^mZT^r  'TS'*^'  ?^^'  ^/"""^  Germany,  $7,850,000;  Switzerland, 
35910,000,  Great  Britam  and  others,  $370,000;  total,  $9,130,000 
,  feince  August  1,  1914,  m  consequence  of  the  outbreak  of  hostilities 
m  J^urope,  this  foreign  supply  has  been  interrupted  and  constantly 
threatened  with  nearly  complete  cessation.  Until  the  present  date. 
German  makers  have  been  able  to  supply  a  considerable  proportion 
ot  the  normal  demands  of  theu-  customers,  but  not  entirely.  Some 
unportant  dyes  are  totally  unobtamable.  Prices  have  mounted  from 
25  to  50  per  cent  on  such  dyestuffs  as  can  be  dehvered.  The  imports 
may  cease  any  day  through  inabihty  to  make  shipments,  on  account 
of  mantmie  dangers,  or  what  is  more  probable,  through  the  mihtary 
necessity  of  comniandeering  the  available  supply  of  the  chief  coal- 
tar  crude  matenal,  benzol,  for  use  as  a  motor  fuel,  or  diverting  the 
limited  supply  of  nitnc  acid— the  chief  chemical  used  in  color  nfanu- 
lacture — to  the  manufacture  of  explosives. 

The  multitude  of  users  of  dyestuffs  in  the  United  States  have 
been  crippled  in  various  ways,  forced  to  change  designs,  or  abandon 
certain  products  or  to  revert  to  a  temporary  use  of  natural  dye- 
stutts,  with  all  the  accessory  readjustment  and  revolution  in  dyeing 
processes.  On  every  hand  there  is  difficulty  in  meeting  contrac! 
specifications  and  m  makmg  definite  plans  and  agreements  for  the 
future.  The  importation  of  dyewood  has  quickly  increased.  It  is 
now  four  times  as  great  as  in  normal  times.  Prices  of  these  dyewoods 
have  niounted.     I  ustic,  for  example,  has  doubled  in  price 

The  four  American  establishments  making  artificial  dyestuffs  have 
done  their  best  to  meet  the  emergency  by  enlarging  the  ordinary 
output.  They  have  been  crippled  by  the  difficulties  or  impossibUity 
of  securing  half-manufactured:  materials  from  abroad  or  crude  ma- 
terials at  home.  Some  large  consumers  of  dyestuffs  have  erected 
emergency  plants  and  make  the  colors  they  absolutely  need,  but  at 
considerable  cost.  j  ,  au 

DOMINANCE   OF   THE   GERMAN   INDUSTRY. 

In  all  this  annoyance,  loss,  and  uncertainty  why  do  we  not  have  an 
American  coal-tar  chemical  industry,  capable  of  meeting  the  Nation's 
demands,  self-contained  and  independent  of  foreign  control  utiliz- 
mg  our  native  raw  material  ?  ' 

A  careful  analysis  of  the  situation  shows  that  not  only  is  the 
American  supply  and  the  limited  American  production  of  coal-tar 
dyestuffs  completely  dominated  by  the  German  industry,  but  that 
this  is  the  case  throughout  the  world.  Even  countries  such  as 
Great  Britain  and  France,  with  ample  supplies  of  crude  material  and 
highly  developed  industrial  power,  are  in  the  same  condition  as  the 
United  States. 

In  1913  the  total  consumption  of  artificial  dyestuffs  in  the  world 
had  attained  a  value  of  over  $92,000,000.  Germany  furnished  74 
per  cent  of  the  entire  amount  and  over  one-half  of  the  materials 
needed  to  make  the  remainder.  The.  only  country,  in  addition  to 
irermany  manufacturing  dyestuffs  in  any  noteworthy  manner  for 
the  world  s  markets  IS  Switzerland.  That  country  rdies,  however 
for  Its  crude  and  half-manufactured  materials  chiefly  upon  German 
sources.    The  dommance  of  Germany  in  the  dyestuff  production  and 


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commerce  of  the  entire  world  is  so  marked,  and  inherently  of  such 
potential  might,  that  it  does  not  hesitate  to  make  itself  felt  when- 
ever and  wherever  an  effort  is  made  toward  emancipation  from  its 
control.  The  methods  used  are  those  often  associated  with  the 
working  of  great  industrial  corporations  in  various  lands  and  now 
effectively  checked  by  legal  enactment  in  the  United  States.  In  the 
case  of  tne  German  coal-tar  chemical  industry,  the  field  is  interna- 
tional and  its  operations  are  unchecked  by  law.  Its  influence  has 
been  felt  at  once  in  our  own  country  when  efforts  to  manufacture 
intermediate  compounds  or  finished  dyes  threatened  in  any  way  the 
interests  of  the  German  production  and  trade. 

ADVANTAGES   POSSESSED   BY   GERMAN   MANUFACTURERS. 

The  coal-tar  chemical  industry  includes  not  only  the  manufacture 
of  dyestuffs,  but  of  a  number  of  valuable  medicinal  preparations,  and 
of  various  high  explosives.  It  is  based  upon  the  use  of  crude  com- 
pounds present  to  a, .small  extent  ia  the  tar  obtained  in  the  de- 
structive distillation.  efcoaTin  gas  works  and  coke  ovens.  These 
10  crude  compounds — benzol,  carbolic  acid,  anthracene,  etc. — are 
separated^  f rom  some  145  other  substances  present  in  tar,  by  frac- 
tionaLdistiUation.  Thisis  the  work  of  the  tar  distiller.  From  the  10 
crudes,  nearly  300  more  complex  compounds,  none  of  them  dyes, 
are  produced  by  highly  refined  and  comphcated  chemical  and  me- 
chanical processes,  involving  in  most  cases  a  number  of  complete 
chemical  transformations.  These  serve  as  the  materials  for  the 
manufacture  of  about  920  dyestuffs  now  in  current  use. 

In  the  case  of  Germany,  the  domestic  supply  of  '^crudes"  is  amply 
sufficient.  The  color  factories  make  aU  of  the  300  intermediates  re- 
c^uired  for  Germany's  own  industry  and  a  large  share  of  those  used 
in  the  very  restricted  production  of  other  lands. 

The  industry  has  been  chiefly  developed  by  the  inventive  power 
of  German  chemists,  combined  with  a  wealth  of  technical  skill  and 
keen  business  management,  scarcely  equaled  in  the  history  of  any 
other  branch  of  manufacture.  The  21  German  companies  engaged 
in  the  dyestuff  manufacture  have  a  nominal  capital  of  over 
$36,700,000  on  which  dividends  average  22  per  cent.  Actual  profits 
often  reach  50  per  cent.  The  great  excesses  have  been  devoted  to 
new  construction.  It  is  the  most  remunerative  industry  in  the 
Empu-e,  the  one  niost  solidly  and  formidably  intrenched,  the  one  of 
which  the  nation  is  most  proud  as  showing  the  triumph  of  science 
applied  to  industrial  purposes,  and  the  one  iQustrating  most  strik- 
i^igly  the  ability  to  wm  and  maintain  international  supremacy  in  a 
given  field. 

ABUNDANCE   OF   AMERICAN   RAW   MATERIAL. 

In  the  United  States  the  supply  of  coal  tar  is  ample,  suflScient  to 
provide  in  abundance  all  of  the  crudes  required  for  the  manufacture 
of  the  dyestuffs  consumed  in  the  country.  The  amount  of  valuable 
by-products  not  yet  recovered  in  our  present  coking  plants  amounts 
to  $75,000,000  annually.  With  adequate  provision  to  save  all  the 
benzol  and  tar  liberated  in  American  coke  ovens,  enough  of  the  10 
crudes  could  be  secured  to  more  than  cover  the  world's  consumption 
in  making  artificial  dyestuffs. 


10 


DYESTUFFS  FOR  AMERICAN  INDUSTRIES. 


If  a  commercial  demand  is  present,  American  tar  works  can 
quickly  provide  all  of  the  crudes  needed,  practically  as  cheaply  as 
in  Europe.  In  the  manufacture  of  intermediates  the  production  is 
restricted  to  four  or  five  compounds,  and  these  cover  about  one- 
quarter  of  the  needs  of  American  color  works. 

Our  manufacture  of  heavy  chemicals  is  well  developed,  able  to 
expand  rapidly,  and  supply  all  needed  chemicals  for  the  production 
of  intermediates  and  theu-  transformation  into  finished  dyes. 

The  four  establishments  devoted  to  the  production  of  dyes  supply 
nearly  100  different  colors,  largely,  however,  as  already  stated,  by 
'^assembling''  nearly  finished  products  of  foreign  origin.  These 
American  firms  are  bold  ana  enterprising,  commanding  about 
$3,000,000  capital,  evidently  doing  the  oest  they  can  under  existing 
conditions  to  build  up  a  national  industry. 

Investigation  shows  that  their  advance,  beyond  certain  limits, 
in  the  manufacture  of  either  intermediate  or  finished  dyes  is  per- 
sistently checked  and  prevented  by  the  united  action  of  German 
producers  in  underselling.  The  entire  German  color  industry  is  so 
completely  organized  and  accustomed  to  act  as  a  unit  in  furthering 
the  general  interests,  at  home  and  abroad,  that  little  success  in  facing 
their  determined  opposition  has  heretofore  been  obtained. 

The  present  crisis  has  evoked  deep  interest  on  the  part  of  all  con- 
cerned— tar  distillers,  manufacturers  of  chemicals,  manufacturers 
of  dyestuffs,  the  many  users  of  the  same,  and  American  economists 
in  general — as  to  how  the  problem  can  be  settled.  There  is  no  ques- 
tion but  that  our  coke  interests  are  ready  to  multiply  their  recovery 
plants  for  the  production  of  benzol  and  tar,  if  a  permanent  market  is 
assured.  There  is  no  question  of  the  readiness  of  tar  distillers  to 
enlarge  their  plants  for  the  production  of  an  ample  supply  of  the 
needed  crudes  if  a  continued  demand  is  certain.  American  chemical 
works  and  American  manufacturers  of  dyestuffs  are  ready  to  embark 
capital  and  experience  in  building  up  a  distinctly  American  coal-tar 
chemical  industry,  using  entirely  American  crudes  and  intermedi- 
ates, provided  there  is  adequate  legislative  prohibition  against  both 
"dumping"  or  unfair  restraint  of  American  trade  by  the  arbitrary 
action  of  foreign  monopoly  permitted  by  foreign  law  and  not  as  yet 
forbidden  by  our  own.  Domestic  maKers  assert  their  ability  to 
make  at  once  over  90  per  cent  of  the  dyes  now  consumed  in  the 
United  States,  which  are  now  patent-free,  and  state  that  the  remain- 
ing tenth  will  soon  be  freed  from  patent  restriction. 

WHAT  THE  AMERICAN  INDUSTRY   REQUIRES. 

There  seems  to  be  a  consensus  of  opinion  that  anv  rapid  develop- 
ment and  evolution  of  the  dyestuff  branch,  on  a  scale  commensurate 
with  the  Nation's  needs,  present  and  prospective,  can  be  assured  only 
on  the  basis  of  an  effective  law  preventing  that  action  toward  con- 
trol of  our  markets  by  a  foreign  monopoly  which  is  now  prohibited 
to  a  domestic  monopoly.  Some  of  the  largest  manufacturers  have 
personally  informed  the  department  that  what  is  needed  is  not  a 
tariff  change,  but  laws  placing  a  foreign  monopoly  on  the  same  basis 
as  an  American  one. 

American  economists  feel  that  the  present  crisis  offers  the  most 
favorable  moment  to  decide  upon  a  policy  with  regard  to  this  one 


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DYESTUFFS  FOR  AMERICAN  INDUSTRIES. 


11 


important  industry,  whether  it  is  to  be  firmly  rooted  in  American 
soil  or  whether  the  dependence  upon  a  foreign  source  is  to  continue 
indefinitely.  It  is  pointed  out  that  each  year  elapsing  increases  in 
geometrical  ratio  the  difficulties  attendant  upon  any  attempt  to  create 
a  self-contained  American  dyestuff  industry.  Further,  it  is  claimed 
that  it  is  the  only  highly  organized  industry  not  yet  brought  on  a 
broad  and  generous  scale  within  the  cycle  of  American  economic 
activity. 

In  England  and  France  the  textile  and  other  branches  have 
insisted  that  the  national  industries  must  be  permanently  freed  from 
dependence  upon  a  foreign  source  for  one  oi  the  vital  needs  of  the 
most  varied  manufactures.  Within  a  fortnight  the  group  of  French 
chemists  intrusted  with  the  problem  claim  that  they  have  satisfac- 
torily solved  aU  difficulties  m  the  way.  During  the  same  period 
the  necessary  steps  have  been  taken  in  England,  where  the  Govern- 
ment has  provided  for  the  organization  of  a  national  company  to 
create  an  independent  dyestuff  industry,  contributing  nearly 
$2,000,000  to  its  capital,  and  granting  at  the  same  time  $500,000  for 
the  requisite  research  laboratory. 


-A 


> 


DYESrUFFS  FOR  AMERICAN  INDUSTRIES. 


13 


DYESTUFF  SITUATION  IN  THE  UNITED  STATES. 

There  is  a  large  and  steadily  growing  consumption  of  dyestuflFs  in 
the  United  States  required  in  a  variety  of  industries.  The  most 
important  of  these  industries  are:  Textiles — cotton,  silk,  woolen,  etc.; 
pamts  and  pigments;  varnishes;  inks;  leather  articles;  feathers. 

A  great  variety  of  industries,  in  addition,  are  closely  dependent 
upon  the  above  for  all  that  concerns  color  effects.  Promment  among 
these  are  the  printing  trades;  automobile  and  carriage  manufacture; 
implement  manufacture;  paper  trade;  soap  trade;  upholstery  trade; 
millinery,  dressmaking,  etc. 

Further,  a  notable  and  increasing  number  of  preparations  made 
from  by-products  and  accessory  products  of  the  manufacture  of 
artificial  dyestuffs  are  now  used  in  photography,  medicine,  the  pro- 
duction of  high  explosives,  and  the  manufacture  of  artificial  per- 
fumes. Economically  these  are  very  closely  interlocked  with  the 
dyes  tuff  industry. 

Directly  and  indirectly,  a  large  proportion  of  American  industries 
are  dependent  upon  a  constant  and  varied  supply  of  dyestuffs. 

DYESTUFFS  USED  IN  THE  UNITED  STATES. 

The  dyestuffs  consumed  by  American  industries  fall  into  three 
classes:  Natural  organic  dyes,  mineral  dyes,  and  artificial  organic 
dyes. 

Until  about  1860  the  dyeing  trades  were  restricted  to  the  use  of 
preparations  falling  in  the  first  two  classes.  Soon  after  that  date  the 
earlier  anihne  colors  were  introduced  into  general  use.  The  number 
and  variety  of  these  artificial  products,  made  from  the  different  con- 
stituents of  coal  tar,  rapidly  increased.  It  was  soon  possible  to 
replace,  in  most  cases  with  very  pronounced  advantages,  every  tint 
and  shade  yielded  by  natural  and  mineral  dyes,  and,  m  addition,  to 
increase  greatly  the  hues  available  for  color  designs  in  a  multitude 
of  industries.  The  use  of  the  older  dyeing  materials,  both  organic 
and  mineral,  quickly  lessened.  To-day,  and  for  some  years  past, 
the  great  bulk  of  the  dyestuffs  consumed  in  the  United  States  con- 
sists of  synthetic  products  of  the  coal-tar  chemical  industry.  The 
dyestuffs  of  an  earlier  day  have  been  in  most  cases  almost  completely 
superseded.  In  a  few  instances  they  play  a  minor  and  humble  r6le, 
chiefly  as  accessories  in  the  use  of  the  artificial  dyes. 

♦■4 

NATURAL  ORGANIC  DYES. 

The  natural  organic  dyes  are  conveniently  classified  in  four  sub- 
divisions: (1)  Indigo;  (2)  logwood;  (3)  red  dyes;  (4)  yellow  dyes. 
(1)  Indigo. — This  substance,  obtained  from  various  plants  of  the 

fenus  Indigofera,  was  for  centuries  the  most  important  of  aU  dyestuffs. 
Intil  quite  recently  it  was  supphed  from  Asiatic  countries,  chiefly 
from  India,  and  to  some  extent  from  tropical  America.  The  natural 
dyes  tuff  is  now  replaced  almost  entirely  by  the  synthetic  product, 
which  has  manifest  advantages  in  uniformity  of  strength  and  shade, 
as  well  as  in  price.  The  amount  of  natural  indigo  now  used  in  the 
United  States  is  about  7  per  cent  of  the  total  amount  of  indigo. 

12 


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(2)  Logwood,— This  dye  is  extracted  from  campeachy  wood,  found 
m  tropical  and  subtropical  America.  Our  supply  comes  ahnost 
entu-ely  from  Jamaica.  The  extraction  of  the  coloring  matter  from 
the  wood  IS  done  usually  in  American  mills,  although  a  certam 
amount  of  extract  is  also  imported.  Next  to  indigo,  logwood  was 
until  the  past  half  century,  the  most  important  dyes  tuff  known  It 
was  universally  employed  for  the  dyeing  of  black  on  aU  classes  of 
fabrics,  as  was  indigo  for  the  production  of  blue.  It  is  to-day  the 
only  natural  coloring  matter,  except  indigo,  employed  extensively 
by  the  dyer.  While  of  limited  application  now  on  cotton  and  wool 
for  the  production  of  very  cheap  blacks,  there  is  stiU  a  large  amount 
used  m  dveing  silk,  to  the  fiber  of  which  it  gives  greater  opacity  than 
can  be  obtamed  from  coal-tar  dyes.  There  is  ako  an  extended  use 
in  dyemg  leather.  Considerable  amounts  are  employed  in  connection 
with  dyestuffs,  m  order  to  tone  shghtly  the  shade  produced. 

(3)  Red  dyes— These  include  among  the  dyewoods,  Brazil  wood 
peach  wood,  Japan  wood,   and  Lima  wood,  which  yield  soluble 
tinctorial  matters;  and  barwood,   camwood,   and  Saunders  wood 
which  contam  msoluble  colormg  substances.     None  of  these  to-dav 
has  more  than  a  very  limited  use.    Most  of  the  woods  in  question 
are  supphed  by  Central  America  and  South  America 

Mad.der,  obtained  from  the  root  of  the  Ruhia  tinctoria,  used  for 
centuri^  to  produce  the  famous  ^'Turkey  red,"  has  now  ahnost  dis- 
appeared from  commerce  Its  coloring  prmciple,  ahzarin,  has  been 
manufactured  synthetically  from  the  anthracene  of  coal  tar  smce 
1871.     A  small  amount  of  the  root  is  still  imported 

Cochineal,  a  brUliant  scarlet,  extracted  from  the  female  of  the 
msect  Coccus  cacti,  found  abundantly  on  the  cactus  plant  in  Mexico 
and  Central  America,  was  once  a  valued  dye  for  woolens,  and  is  still 
employed  to  dye  the  uniforms  of  the  British  army.  It  resisted 
longer  than  madder  the  invasion  of  artificial  dyestuffs,  but  its  use 
m  the  Umted  States  is  now  very  limited. 

,  OrchU  and  its  dried  extract,  cudbear,  found  very  extensive  use 
in  producmg  purphsh-red  and  reddish-brown  shades  on  wool  and  on 
sUk.  It  IS  extracted  from  lichens,  found  in  abundance  on  the  sea- 
coasts  of  subtropical  countries.  Lower  California  formerly  yielded 
great  quantitie^  At  present  the  use  is  restricted  and  Umited  chiefly 
to  tonmg  the  effects  produced  by  other  dyes. 

Annatto  from  the  fruit  of  the  Bixa  oreUana,  in  South  America, 
has  a  Imuted  application  m  silk  dyeing.     It  is  more  largely  used  to 

Safflower,  the  dried  florets  of  Carthamus  tinctonus,  has  a  very 
.  slight  use  for  imparting  pmks  to  cheap  cottons. 

(4)  Yelhw  dyes.— The  principal  yellow  dye  is  fustic,  obtained  from 
the  wood  of  Morus  tinctona,  a  tree  occurring  abundantly  in  the 
West  Indies  and  Central  and  South  America.  Formerly  used  largely 
for  yellows  and  ohves,  it  now  finds  a  hmited  employment  for  tomnk 
logwood  effects,  especially  on  woolens.  ^^ 

^n!ifc^^^^      extracted  from  a  species  of  oak  in  the  Middle  and 
Southern  States,  still  has  a  limited  use  in  cahco  printing 

frn^^?i?n  -^T'^  ^^?  """^'^.^  ^^^j.^^,  ^^  ^^^  buckthorn,  imported 
from  the  Orient  are  also  used  to  a  shght  extent  for  calico  printing. 

a  iJi™^T'-  ^.^^r^^^ed  from  Curcuma  tinctoria,  an  Asiatic  rootTlias 
a  very  restricted  use,  chiefly  in  producing  composite  shades 


14 


DYESTUFFS  FOR  AMERICAN  INDUSTRIES. 


Cutch,  obtained  from  an  Indian  variety  of  acacia,  is  employed 
slightly  for  a  few  brown  shades,  but  more  extensively  as  a  tannin 
mordant  on  cottons. 

The  displacement  of  these  natural  dyes  by  artificial  colors  was  not 
due  entirely  to  the  fact  that  the  latter  could  often  be  manufactured 
more  cheaply.  Most  of  the  vegetable  dyes  were  far  removed  from 
being  pure  dyestuffs.  The  extracts  obtamed  from  woods  and  plants 
contained,  in  addition,  a  variety  of  non-tinctorial  substances,  resins, 
tannins,  sugars,  pectinous  bodies,  etc.  It  was  practically  impossible 
to  isolate  the  pure  coloring  matter.  As  a  consequence,  the  extracts 
varied  seriously  in  their  strength,  and  the  colors  imparted  were  dull. 
The  processes  of  dyeing  became  easier,  simpler,  and  cheaper,  and 
could^be  readily  standardized.  It  was  furtner  possible  to  extend 
greatly  the  range  of  colors.  Many  tones  and  shades,  hitherto  un- 
known, were  at  the  service  of  the  dyer.  Most  important  of  all  was 
the  fact  that  the  artificial  dyestuffs,  as  a  rule,  were  fast  as  compared 
with  most  of  the  natural  colors.  Indigo  was  the  fastest  color,  and 
still  represents  the  standard  for  comparison.  Madder  was  practically 
as  fast,  but  neither  could  be  obtained  from  their  vegetable  sources  in 
a  form  at  all  pure  or  approaching  uniformity.  The  synthetic  prod- 
ucts were  pure  and  of  uniform  strength.  Cochineal  was  a  fairly  fast 
color,  faster  than  the  earher  coal-tar  scarlets;  and  although  the  latter 
were  cheaper,  the  animal  dyestuff  held  its  own  until  the  appearance 
of  anthracene  and  chrome  scarlets,  which  possessed  even  higher  de- 
grees of  permanence. 

The  otner  natural  dyestuffs  enumerated  above  were  highly  fugitive, 
as  compared  with  the  corresponding  coal-tar  colors,  which  appeared 
in  rapid  succession  from  1860  on.  Logwood  was  fast  to  washing,  but 
not  very  resistant  to  Hght  or  on  exposure  to  weather.  It  held  its 
own,  however,  until  the  appearance  oi  the  fast  alizarin  blacks.  Even 
now  it  is  employed  largely  for  cheap  grades  of  cotton  and  woolen, 
and  is  the  one  natural  dyestuff  that  continues  to  maintain  a  rela- 
tively important  position  m  the  dveing  branch. 

With  regard  to  the  sources  of  the  natural  organic  dyestuffs,  it  will 
be  noticed  that  the  present  supply  of  the  United  States  is  chiefly 
drawn  from  the  tropical  and  subtropical  regions  of  the  Western 
Hemisphere.  A  few  materials — natural  indigo,  cutch,  Persian  berries, 
madder,  and  turmeric — come  from  Asia.  A  single  dyestuff,  quercit- 
ron, is  indigenous  to  the  United  States. 

IMPORTATION  OF  NATURAL  ORGANIC  DYES. 

The  following  table  gives  the  quantity  and  value  of  the  imports  of 
natural  organic  dyestuffs  into  the  United  States  for  the  fiscal  year 
ending  June  30,  1913: 


1 


Articles. 


Quantity. 


Vahie. 


Annatto pounds. . 

Camwood 

Cochineal pounds. . 

Cudbear do — 

Dyewoods,  diverse tons. . 

Fustic  wood do — 

Indigo,  natural iwunds. . 

Logwood tons. . 

Logwood  (and  other  wood)  ex- 
tracts  pounds.. 


405,024 


109,089 

27,971 

155 

3,785 

231,834 

36,952 

2,258,206 


S19,991 

191 

44,249 

1,755 

1,794 

53,303 

88,716 

475,484 

111,575 


Articles. 


Quantity. 


Madder,  ground pounds. 

Madder,  extract do. . . 

Orchil 

Persian  berries,extract  pounds. 

SaflSower,  saflron 

Turmeric 


Total. 


30,602 
2,154 


64,883 


Value. 


$2,803 
233 
27,386 
7,173 
03,146 
33,735 


961,534 


<r 


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DYESTUFFS  FOE  AMEBICAN   INDUSTRIES. 


MINEBAL  DTES. 


15 


The  use  of  inorganic  coloring  materials  for  the  production  of  dyeing 
effects  by  direct  precipitation  m  the  fibers  of  textiles  was  formerly  of 
considerable  importance.  Most  of  the  processes  once  in  vogue  are 
now  completely  obsolete.  The  few  still  in  occasional  use  are  of  minor 
value  and  limited  appUcation.  They  are  comprised  in  the  following 
list: 

Chrome  yellow  and  orange. — ^These  are  dependent  upon  the  use  of 
lead  acetate  and  potassium  bichromate. 

Iron  huff. — Obtained  by  the  precipitation  of  ferric  hydroxide  from 
soluble  iron  salts. 

Iron  gray. — Obtained  by  the  precipitation  of  tannate  of  iron  from 
soluble  salts. 

Manganese  brown. — Precipitation  of  manganic  oxide  from  soluble 
manganese  salts. 

Chrome  areen. — Obtained  by  the  use  of  chrome  alum.  In  combi- 
nation with  iron  buff  this  is  now  employed  to  some  extent  to  produce 
the  popular  khaki  effects. 

Prussian  blue.— Oht&med  by  the  use  of  potassium  ferrocyanide 
and  soluble  iron  salts.  There  is  a  somewhat  extended  use,  in  connec- 
tion with  other  coloring  materials,  for  the  dyeing  of  silk. 

Most  of  the  mineral  dyestuffs  enumerated  above  are  currently 
manufactured  in  the  United  States.  Manganese  compounds  are, 
however,  usually  imported  from  Europe,  and  potassium  ferrocyanide 
is  chiefly  of  foreign  origin.  In  1913  the  import  of  this  salt  from 
Europe  reached  a  value  of  $309,000. 

ARTIFICIAL   ORGANIC  DYES. 

The  great  volume  of  the  dyestuffs  consumed  by  American  indus- 
tries to-day  consists  of  organic  compounds,  usually  of  very  complex 
composition,  the  raw  materials  for  which  are  found  in  the  products 
of  the  destructive  distillation  of  coal,  as  carried  on  in  the  retorts 
of  gas  works  or  ovens  for  manufacturing  coke.  As  already  men- 
tioned, the  first  of  these  artificial  dyestuffs  appeared  a  httle  over 
half  a  century  ago,  and  rapidly,  one  after  another,  the  natural 
organic  dyes  and  the  mineral  dyes  were  displaced  from  their  posi- 
tions and  reduced  to  minor  and  subordinate  rank,  if  not  forced  to  dis- 
appear completely  from  use. 

The  consumption  of  the  artificial  coal-tar  colors  in  the  United 
States  has  now  assumed  large  dimensions.  The  increase  in  this 
consumption  keeps  even  pace  with  the  growth  of  American  manu- 
facturing industries,  and  more  especially  with  the  development  of 
the  various  textile  branches. 

It  has  been  of  far-reaching  influence  in  determining  the  expansion 
of  cotton  manufacture.  While  wool  and  silk  were  dyed  with  com- 
parative facility  by  vegetable  dyes,  the  contrary  was  the  case  with 
cotton  wares.  The  inert  character  of  the  cotton  fiber  toward  tinc- 
torial substances,  and  the  diflSculty  of  mordanting  it  with  metaUie 
salts,  caused  a  serious  limitation  in  the  range  of  colors  and  processes 
available  for  dyeing  cotton  materials,  and  greatly  restricted  their  use. 
The  discovery  of  aniline  dyes,  capable  of  dyeing  cotton  directly, 
was  a  notable  step  forward,  despite  the  fact  that  these  earlier  prod- 
86201°— 15 2 


\ 


16 


DYESTUFFS  FOR  AMERICAN  INDUSTRIES. 


ucts  were  not  very  fast,  and  could  not  be  employed  on  fabrics  requir- 
ing much  laundering.  The  later  discovery  of  the  fast  vat  dyes  of 
the  indigo  class  removed  this  restriction  on  the  use  of  colored  cotton 
goods  lo-day  cotton  can  be  dyed  in  every  variety  of  tint,  and 
the  colors  are  practically  fast,  as  permanent  as  the  fiber  itself.  This 
Has  led  to  an  enormous  development  in  cotton  manufacture,  and  the 
products  are  employed  more  and  more  extensively  in  household 
economy  and  for  wearing  apparel. 

The  great  bulk  of  the  artificial  dyes  is,  however,  used  on  woolen 
fabrics.  Ihese  can  not  be  washed  frequently  without  suffering  from 
shrinkage  and  m  other  ways.  Hence,  if  intended  for  artides  of 
apparel  and  the  hke,  they  are  almost  always  dyed,  and  usually  in 
rather  dark  colors.  This  means  large  quantities  of  dyestuff.  The 
same  rule  apphes  to  the  vast  amounts  of  woolen  material  absorbed 
by  the  carpet,  rug,  and  upholstery  industries.  Such  wares  require  a 
great  consumption  of  acid  dyes,  indigo,  and  the  alizarin  colors,  with 
smaller  amounts  of  the  other  fast  vat  dyes.  Most  of  the  latter, 
mvolvmg  apphcation  m  strongly  alkaline  solutions,  are  in  conse- 
quence not  adapted  for  use  on  wool  fibers. 

The  gre^at  diversity  of  the  modem  demands  for  colored  textiles 
paper,  and  the  like,  has  called  for  equal  diversity  in  the  dyestuffs 
employed,  not  only  as  regards  color,  but  also  as  regards  fastness  to 
bght  or  washmg. 

At  present  the  American  demand  calls  for  over  900  different  arti- 
ncial  dyestuflFs.  A  small  group  includes  colors  used  in  very  largo 
amounts.  In  another  much  more  numerous  group  fall  colors  em- 
ployed m  moderate  but  still  noteworthy  quantities.  The  majority 
of  the  dyes  enumerated  in  current  price  lists  are  demanded  in  smaU 
amounts  and  for  special  purposes  or  qualities.  This  third  category 
includes  most  of  the  very  high-priced  dyestuffs.  The  necessity  of 
providing  the  great  variety  of  colors  found  in  this  category  is  a 
dommant  factor  in  the  dyestuff  industry. 

1X)MESTIC    MANUFACTURE    OF   ARTIFICIAL   DYESTUFFS. 

The  demand  for  artificial  dyes  in  the  United  States  is  met  to  some 
extent  by  the  domestic  coal-tar  dye  industry.  The  great  bulk  of 
dyes  used,  however,  is  imported  from  Europe,  Germany  bemg  the 
chief  source. 

It  is  not  easy  to  estimate  the  value  of  the  current  annual  produc- 
tion m  the  United  States  of  coal-tar  dyestuffs.  Estimates  furnished 
by  those  en^ged  in  the  manufacture  range  from  $2,000,000  to 
$5,000,000.  The  census  report  of  1909  gives  $3,462,000  as  the 
value  of  artificial  dyestuffs  produced  in  that  year.  Among  our 
exports  of  domestic  manufacture  there  has  been  for  five  years  an 
average  export  of  'Myes  and  dyestuffs''  amounting  to  $345,000.  It 
IS  doubtful  whether  artificial  dyestuffs  constitute  any  appreciable 
share  of  this  item,  a  large  portion  of  which  goes  to  Canack.  It  is 
probable  that  the  American  consumption  of  artificial  dyes  of  do- 
mestic origin  does  not  vary  much  from  $3,000,000  per  annum. 

The  returns  of  our  forei^  commerce  for  the  fiscal  years  ending 
June  30,  1909-1914,  give  the  following  values  for  the  imports  into 
the  United  States  of  coal-tar  dyestuffs : 


V 


A 


I 


•/ 


6 


C 


^ 


** 
w 


» 


V 


»  ) 


DYESTUFFS  FOE  AMERICAN   INDUSTRIES. 


17 


Articles. 

1900 

1910 

1911 

1912 

1913 

1914 

Aliiarin  and  alizarin  dyes 

Artificial  indipo 

$1,215,700 
1.242,149 
5,901,842 

?647,944 
1,045,375 
6,011,054 

$708,346 
1,009,709 
6,022,986 

$1,381,936 
1,017,516 
6,965,121 

$1,817,270 
1,014,181 
7,105,284 

$845,459 

other  coal-tar  dyes 

1,015,201 

7,241,406 

Total 

8,359,691 

7,704,373 

7,741,041 

9,364,573 

9,936,735 

9,102,066 

Ahzarin  and  mdigo  and  their  derivatives  are  imported  duty  free 
Other  artificial  dyes  pay  a  duty  of  30  per  cent.  The  figures  for  indi<To 
do  not  include  natural  indigo  from  Asia,  and  from  British  porte 
Ihe  annual  value  of  the  imports  of  natural  indigo  has  sunk  from 
$158,000  in  1909  to  $78,000  in  1914.  Coal-tar  dyes  paid  in  1913 
duties  amounting  to  $2,071,000  and  in  1914  to  $2,261,361.  There 
IS  a  small  export,  chiefly  to  Canada,  of  foreign-made  artificial  dves 
Its  value  in  1913  was  $46,249,  and  in  1914  $38,257. 

The  German  official  statistics  for  the  calendar  year  1913  give  the 
export  of  dyes  to  the  United  States  as  $9,030,000,  and  the  imports 
of  such  wares  from  the  United  States  as  $12,000. 

The  average  annual  value  of  the  imports  of  coal-tar  dves  during 
w^.u  ^1^5^®  y^^"^  '^^.  ^8,781,736.  this  is  the  cost  price  abroad 
With  added  amounts  paid  for  duties,  about  $2,000,000,  and  expenses 
and  profats,  the  sum  annually  expended  for  foreign  coal-tar  dves 
exceeds  $12,000  000.  Assuming  the  value  of  the  colors  manufac- 
«^'*nnnnnn  ^f^P^^^d  in  the  United  States  to  be  approximately 
$3,000  000  it  IS  found  that  American  consumers  are  now  pavini 
annually  about  $15,000,000  for  coal-tar  dyes.  f  j-^ 

FOREIGN  SOURCES  OF  ARTIFICIAL  DYESTUFFS. 

If  the^  general  imports  of  coal-tar  dyes  into  the  United  States  are 
analyzed  as  to  country  of  origin,  the  foUowing  is  found  to  be  the 
case  for  the  imports  of  1913:  Of  ahzarin  and  derivatives,  Germanv 
supphes  99  per  'cent;  of  synthetic  indigo,  Germany  supplies  96  per 
cent  and  Switzeriand  2.4  per  cent;  of  other  coal-tar  dyes,  Germanv 
supplies  81  per  cent,  Switzerland  12  per  cent,  the  United  Kmgdom 
2.8  per  cent,  Belgium  2.5  per  cent,  and  France  1.0  per  cent. 

orilirf  "^^/f  .  ?""  i^^^^iT  'A  ^"PP«.^^d  t«  be  largely  of  German 
ongm.  The  total  value  of  the  German  unport  in  1913  was  $8,538,000. 
It  constituted  86  per  cent  of  the  value  of  imported  artificial  dyestuffs. 
iJ^^   r^^  import  reached  $918,232.     It  formed  9  per  cent  of  the 

if  ^  Jf  i"  I  7v!^^  TT  -f?  o^^^'  ^P?^^  ^^^"^  ^^^  ^^d^st  contribution 
of  Switzerland,  the  United  States  depends  almost  entirely  on  Ger- 
many for  its  supply  of  imported  artificial  dyestuffs. 

ECONOMIC  EFFECTS  OF  DEPENDENCE  UPON  A  SINGLE  FOREIGN  SOURCE. 

The  economic  dependence  of  the  United  States,  and  in  fact  of  aU 
nations,  upon  a  smgle  foreign  source  for  the  regular  supply  of  an 
important  class  of  manufactures  is  comparable  iit  many  respects  to 

monopoU^         "^"''  Geimany  for  potash,  aU  three"^  being  natural 


18 


DYESTUFFS  FOR  AMERICAN  INDUSTRIES. 


The  danger  inherent  to  such  a  state  of  dependence  has  been  sharply 
brought  to  view  in  the  world-wide  experience  of  the  last  seven  months. 
Some  countries  have  been  deprived  almost  entirely  of  their  customary 
supplies  of  artificial  dyes.  In  others,  notably  in  our  own  land,  the 
supply  has  been  intermittent  and  its  continuance  xmcertain. 

Thousands  of  American  industrial  plants  and  an  armv  of  opera- 
tives, with  their  dependents,  have  been  threatened  with  a  serious 
arrest  of  manufacturing  activities.     In  manv  cases  it  has  been  im- 

f)ossible  to  fill  contracts ;  in  a  multitude  of  instances  managers  of 
arge  establishments  have  had  to  grapple  seriously  with  the  problem 
of  now  to  continue  manufacture  with  Hmited  supplies  or  with  no 
supphes  of  the  customary  coloring  matters. 

Fortunately,  after  the  first  excitement  following  the  outbreak  of  hos- 
tihties,  in  August,  1914,  and  the  interruption  for  some  weeks  of  all 
shipments  of  foreign  dyestuffs,  means  were  found  to  resume  the  ex- 
portation from  Germany  and  Switzerland.  By  the  close  of  1914  most 
American  manufacturers  had  been  supphed  with  the  majority  of  their 
customary  supphes  of  coal-tar  dyes  m  nearly  normal  amount. 

On  August  1,  1914,  the  textile  works  had  supplies  adequate  for  the 
needs  of  their  miUs  ^or  two  or  three  months.  The  German  Govern- 
ment granted  permission  for  the  monthly  export  to  the  United  States, 
in  American  vessels,  of  a  maximum  allowance  of  2,300  tons  of  artificial 
dyestuffs. 

The  result  has  been  that,  while  a  few  cases  of  hardship  were  una- 
voidable, and  here  and  there  changes  in  style,  etc.,  were  required, 
textile  branches  have  not  materially  suffered  thus  far. 

INCREASED   COST   OF   COAL-TAR  DYES. 

There  has  been  an  increase  in  the  cost  of  dyes,  naturally  inevitable 
with  the  rise  in  freight  rates  and  insurance.  In  September,  1914, 
the  average  increase  on  foreign  dyes  was  estimated  at  about  25  per 
cent.  Since  then  there  has  been  a  rise  of  about  the  same  amount. 
The  price  of  ahzarin  is  now  about  50  per  cent  above  that  of  August, 
1914.  In  some  instances  very  abnormal  rates  are  quoted.  Sen- 
zopurpurin,  an  important  cotton  dye,  seUing  ordinarily  at  14  cents 
per  pound,  is  now  (Mar.  15)  quoted  at  80  cents. 

American  manufacturers  of  dyes  have  been  able  to  retain  old 
rates  on  about  one-third  of  their  products,  while  the  prices  of  the 
rest  have  doubled  in  consequence  oi  the  increased  cost  of  raw  mate- 
rial. In  general,  there  has  been  a  pleasant  concurrence  of  opinion 
on  the  part  of  American  consumers  oi  dyestuffs  that  the  few  American 
manufacturers  in  this  branch  have  taken  no  undue  advantage  of  the 
critical  situation,  and,  further,  that  the  resident  agents  of  foreign 
makers  have  shown  great  resolution  and  energy  in  seeking  to  secure 
supphes  for  their  regular  customers  and  in  distributing  equitably 
such  as  have  been  received. 

OUTLOOK  FOR  THE  IMMEDIATE  FUTURE. 

While  nearly  enough  coal-tar  dyes  are  now  being  shipped  from 
Germany  to  meet  the  current  needs  of  American  consumers,  the 
fact  is  not  disguised  on  either  side  of  the  ocean  that  at  any  moment 
this  supply  may  be  largely  or  totally  suspended.  Several  factors 
enter  here  into  consideration.    Naval  operations  in  the  existing  war 


•\ 


V 


"  ~f 


I 


s 


\ 


'.rv 


I. 


DYESTUFFS  FOE  AMERICAN  INDUSTRIES. 


19 


may  assume  such  a  character  that  maritime  connections  with  the 
port  of  Rotterdam  may  be  completely  severed.  There  is  in  this  case 
a  possibility  of  utilizing  an  Italian  port,  such  as  Genoa,  from  which 
small  amounts  of  dyes  have  already  been  shipped  to  New  York 

Ihe  Gennan  supply  of  benzol  may  be  commandeered  for  use  in 
motors  in  place  of  gasohne.  Benzol  is  the  raw  material  absolutely 
essential  for  the  manufacture  of  the  majority  of  anUine  dyes 

,r.on.ff  f™*°r^°''T"'^^"*  'T^y  '"^l"''"^  f"""  miUtary  purpos^,  in  the 
manufacture  of  explosives,  the  entire  avaUable  stocg^  of^nitric  acid. 
This  would  be  practically  equivalent  to  closing  nearly  every  factory 
engaged  m  mating  dyestuffs.  There  is  hardly  a  dyi  made  excedt 
ahzarin,  in  the  manufacture  of  which  nitric  acid  is  not  required 

home  classes  of  dyestuffs  may  be  crippled  in  their  manufacture  by 
the  lack  of  an  important  raw  material.     CarboUc  acid  is  used  in  largi 

""il?"?*^  t^  *^^j  manufacture  of  explosives.  It  is  also  indispen- 
sable for  the  production  of  a  variety  oi  dyes  muispen 

It  IS  thus  evident  that  any  prolongation  of  the  existing  war  increases 
the  probabibties  of  a  serious  famine  in  artificial  dyestuls. 

ALTERNATIVES  IN  CASE  OF  A  DTESTUFF  FAMINE. 

fl„^?r"''^'fi  ^^'^^  ""^  ^''^i!?  ^°^^  ^I'o  ^a^e  studied  the  problem 
find  three  outlets  from  the  dilemma:  ^  ""lem 

t^  1^  I  '^^^  **/^*'!^  industries  may  be  forced  to  put  upon  the  market 
to  a  large  extent,  goods  that  are  undyed.     This  woufd  be  an  unsat^ 
factory  solution      The  demand  for  such  goods  would  certaiXfS 
below  the  normal,  and  there  would  be  a  serious  drop  in  prices 
ofnffl  ^Z*'"'"''  "?*y  be  made  temporarily  to  the  use  of  natural  dye- 
stuffs      In  some  mstances  vegetable  substitutes  can  be  obtained  with 
Thfnnl^  ^T^'\    This  would  be  particularly  the  case  with  W^d 
The  output  can  be  quickly  mcreased  and  provision  made  for^yeW 
black  on  both  cottons  and^  woolens,  although  at  the  sacrifice  ofS 
ne^.     Fau-ly  ample  supphes  of  orchil  can  be  secured  at  short  noticS 
and  can  be  used  for  reds  and  browns  in  dyeing  carpets  and  wo£ 
generaUy.     There  would  also  be  no  great  aela|  in  o^btamingTstodk 
of  yel  ow  woods.    Considerable  time^would  be^lost,  however  bei^re 
the  coloring  matters  could  be  extracted  and  properly  treatldn  order 
to  develop  desu-ed  strength  and  quality,     fn  tL  case  of  hXo  and 
rt«  fnir^ff*  years  would  elapse  before  the  needed  st<,clS^3d  ^ 
obtamed      It  would  be  scarcely  possible  to  collect  more  than  a  fra^ 
tion  of  the  cochineal  require/  for  scarlets.     The  majority  of  tkte 
now  m  cominon  use  coulS  not  be  produced  at  all.     N^edlL  to  s^v 
there  would  be  myolved  a  revolutU  in  the  methods  of  d™ing      ^' 

(3)  The  attempt  could  be  made  to  build  up  rapidly  an  American 
coal-tar  dyestuff  mdustry,  self-contained  and  iidependei^  b^ed 
upon  the  use  of  American  raw  materials,  and  nroviW^eri^an 
consumers  with  aU  needed  artificial  dyestuffs.  this  woufd^Sv 
demand  some  time,  but  would  insure  pirmanent  freedom  in  the  futS 
llZ^l      "^''^  ***  ^^''^  "^  "^^^y  "^  °"^  g^«*t  industries  are  now 

The  desirability,   and  even  urgency,  of  adopting  the  necessarv 
measures  for  the  creation  of  such  a  national  ind^strf  have  beeTad^ 


^li 


20 


DYESTUFFS  FOB  AMEMCAN  INDUSTRIES. 


It  seems  proper  here  to  consider  why  such  a  complete  industry  has 
not  yet  been  estabhshed  in  the  United  States,  and  under  what  con- 
ditions it  can  be  called  into  existence.  This  involves  a  study  of  the 
existing  coal-tar  chemical  industry  in  the  United  States,  its  limita- 
tions, and  its  successes,  and  a  stuciy  of  the  German  coal-tar  industry, 
with  the  explanation  of  its  present  technical  and  commercial  domi- 
nation in  the  world's  trade. 

OUTLINE  OF  THE  COAL-TAR  CHEMICAL  INDUSTRY. 

When  coal  undergoes  destructive  distiUation  in  coke  ovens  or  gas 
retorts,  the  average  products  are  as  follows:  Coke,  72  per  cent;  gas, 
22  per  cent;  tar,  6  per  cent. 

The  tar  contains  some  155  different  chemical  compounds,  none  of 
which  are  dyes.  Ten  of  these  substances  are  utilized  in  the  manu- 
facture of  dyestuffs.  They  are:  Benzol,  toluol,  xylol,  phenol,  cresol, 
naphthalene,  anthracene,  methyl  anthracene,  phenantnrene,  and  car- 
bazol.  The  first  three  are  present  to  a  considerable  extent  in  the 
crude  gas,  given  off  on  distillation.  Only  by  the  use  of  specially 
designed  purifiers  can  they  be  removed  or  separated. 

The  10  substances  enumerated  form  6  to  12  per  cent  of  the  coal 
tar,  the  amounts  varying  according  to  the  character  of  distillation. 
The  average  yield  is  about  as  follows: 


Sul)stances. 


Benzol,  toluol,  xylol 

Phenol,  cresol 

Naphthalene 

Anthracene  and  remaining  compounds 


Percent- 
age of 
coal. 


0.115 
.015 
.357 
.012 


These  10  primary,  or  crude,  coal-tar  products  are  separated  from 
one  another,  and  from  the  great  variety  of  carbon  compounds  accom- 
panying them  in  the  tar,  by  fractional  distillation.  This  operation 
is  carried  on  in  the  tar  distilleries,  which  supply  likewise  pitch,  creo- 
sote oil,  naphtha,  and  other  crude  mixtures  of  coal-tar  constituents. 

From  the  10  primary  '' crudes,"  chemical  works  of  a  high  charac- 
ter prepare  nearly  300  so-called  ''intermediates,"  compounds  that 
are  not  dyes,  but  which  are  susceptible  by  direct  reactions  of  being 
transformed  into  coloring  matters.  A  number  of  these  intermediates 
serve  also  in  the  manufacture  of  medicinal  preparations,  photo- 
graphic chemicals,  etc.  Leading  intermediates  are  aniline  oil  and 
salts,  pure  aniline  and  toluidine,  nitrobenzol,  naphthol,  phthalic  acid, 
salicylic  acid,  resorcin,  anthraquinone,  etc.  These  intermediate 
products  serve  as  the  raw  material  for  the  manufacturer  of  dyes. 
From  them  he  makes  over  900  different  dyestuffs  now  currently 
sold  in  the  world's  markets. 

In  a  general  way  it  may  be  stated  that  the  average  intermediate 
sells  for  five  times  as  much  as  the  average  crude  coal-tar  derivative, 
and  the  average  finished  dye  for  ten  times  as  much,  a  very  material 
enhancement  in  value. 

The  number  of  intermediates  now  in  active  use  does  not  exhaust 
the  possibihties  in  this- class.  Many  hundred  more  are  known  to  the 
chemist  and  can  be  employed  in  aye  manufacture.     Less  than  300 


J 


•A 


i 


J'\ 


\ 


•c 


DYESTUFFS  FOR  AMERICAN  INDUSTRIES. 


^1 


have  been  found  sufficient  to  meet  the  needs  of  makers  and  to  com- 
bine technical  with  economic  advantages. 

The  same  m^  be  said  of  finished  dyes.  The  number  of  possible 
distinct  dyestuffs  covered  by  patent  specifications  up  to  the  present 
would  run  into  the  milfions.  Of  the  many  possibilities  only  900  have 
won  a  recognized  position,  and  of  these  only  400  are  of  very  extended 
use. 

It  is  doubtful  whether  many  additions  of  value  will  be  made  to  the 
current  fist  of  artificial  dyestuffs  in  the  immediate  future.  The  fidd 
has  been  worked  most  thoroughly  bv  color  chemists.  During  the 
past  decade  only  a  single  new  class  of  dyes  has  been  discovered  and 
placed  on  the  market. 

Briefly  summarizing  the  coal-tar  dyestuff  industry,  the  following 
features  are  obviously  essential  to  success: 

The  presence  of  an  am|)le  supply  of  coal. 

The  extensive  use  of  this  coal  for  gas  and  coke  manufacture. 

The  use  of  a  plant  that  allows  the  recovery  of  the  volatile  organic  compounds  formed 
during  destructive  distillation. 

The  industrial  treatment  of  the  tar  produced,  so  as  to  separate  and  furnish  in  a 
fairly  pure  form  10  crude  substances. 

The  existence  of  well-eauipped  chemical  works,  able  to  transform  the  10  crudes 
into  nearly  300  more  complex  intermediate  compounds. 

The  existence  of  highly  organized  works  for  manufacturing  from  these  intermediates 
some  900  different  dyestuffs. 

An  ample  and  sure  supply  of  a  variety  of  acids  and  heavy  chemicals  for  effecting 
the  numerous  transformations. 

A  relatively  large  number  of  chemists  who  have  enjoyed  university  training. 

COAL-TAR  DYE  INDUSTRY  IN  THE  UNITED  STATES. 

Considering  the  natural  resources  and  economic  conditions  of  the 
United  States,  it  could  reasonablv  be  expected  that  a  well-developed 
coal-tar  chemical  industry  would  flourisn  here. 

The  coal  supply  is  abundant.  The  unmined  coal  deposits  are  five 
times  greater  than  the  reserves  of  Europe.  Large  amounts  of  coal 
are  used  in  furnishing  an  illuminant  and  fuel  for  a  population  of 
100,000,000.  Still  larger  amoimts  are  consumed  in  providing  coke 
for  the  enormous  iron  and  steel  industry. 

The  consumption  of  artificial  dyestuffs  is  large — about  $15,000,000 
in  value  annually,  as  alreadv  noted. 

The  many  universities  and  schools  of  science  are  furnishing  yearly 
a  considerable  number  of  weU-equipped  yoimg  chemists. 

Nearly  all  of  the  world's  great  industries  are  encountered  in  the 
United  States,  finely  developed,  with  high  standards  of  efficiency. 

And  yet,  despite  these  favoring  conditions,  the  production  of  arti- 
ficial dyestuffs  in  the  United  States  is  hardly  half  of  that  manufactured 
in  Switzerland,  a  small  country  without  a  coal  mine. 

SLOW   DEVELOPMENT   OF   THE    AMERICAN    INDUSTRY. 

The  first  aniline  dve,  mauve,  was  discovered  by  Perkins,  in  England, 
in  1856.  It  was  followed  in  the  same  year  by  magenta  and  fuchsine, 
and  the  manufacture  began  in  England  on  a  sm^Ql  and  not  very  re- 
munerative scale.  Little  progress  was  made  imtil  the  appearance,  in 
1862,  of  the  soluble  blues.  Then  followed  in  1863,  Hoffman's  violet 
and  Bismarck  brown;  in  1864,  naphthol  yellow;  in  1867,  the  nigro- 
sines. 


II 


22 


DYESTUPFS  FOR  AMERICAN  IKDUSTRrES. 


i 


DYESTUPFS  FOR  AMERICAN  INDUSTRIES. 


23 


The  manufacture  was  taken  up  with  great  energy  in  both  Germany 
and  b\^tzerland.  A  vast  amount  of  patient,  intelligent,  and  careful 
research  was  expended  upon  the  new  field.  The  industry  was  started 
mi^  ranee  and  England,  but  with  less  zeal  and  scientific  research. 

In  1871  artificial  alizarin  appeared,  and  a  few  years  later  saw  the 
discovery  of  chrysoidme,  malachite  green,  eosine,  and  a  number  of  the 
current  standard  dyes.  The  manufacture  was  growing  rapidly  in 
Germany  and  becoming  well  intrenched. 

During  this  period  the  consumption  of  aniline  dyes  assumed  lar<'o 
proportions  m  the  United  State,  which  became  the  leading  customer 
of  the  German  factories. 

There  seemed  a  good  opening  for  American  enterprise,  and  in  1879 
the  firet  establishment  for  the  manufacture  of  artificial  dyestuffs  was 
started  at  Buffalo.  Eight  others  were  opened  soon  after.  At  that 
time  the  manufacture  was  based  upon  the  use  of  the  intermediates 
imported  from  Europe.  It  was  difficult  to  obtain  an  adequate  supply 
of  benzol  from  domestic  tar  works.  The  Buffalo  works  did  for  a  few 
years  beginning  with  1884,  make  its  own  anihne  oil,  but  was  forced 
to  abandon  the  attempt  on  account  of  the  imcertainty  of  obtaining 
the  raw  material.  ^ 

The  industry  was  exceedingly  remunerative  at  the  outset.  There 
seemed  to  be  a  eood  prospect  of  soon  becoming  independent  of  other 
nations  m  this  branch,  except  so  far  as  patent  protection  existed, 
although  for  the  time  being  the  industry  was  based  upon  the  use  of 
intermediates  of  foreign  origin,  procured  from  Germany  and  Great 
Britain. 

In  1883,  however,  the  growth  of  the  industry  was  suddenly  checked. 
Withm  a  year  five  of  the  nine  estabhshments  were  forced  to  close 
The  other  four  continued  to  manufacture  on  a  close  margin.  These 
four  havmg  been  carefully  conducted,  have  gradually  developed  and 
now  seem  to  be  flourishing.  The  capital  invested  is  estimated  at 
$2,000,000  to  $3,000,000  and  the  annual  output  is  about  $3,000,000 
There  is  not  much  competition  between  the  different  firms,  each'spe^ 
ciahzmg  to  some  extent,  one  for  woolen  dyes,  another  for  cotton 
another  for  paper,  etc.  AU  have  to  meet  keen  competition  on  the 
part  of  the  representatives  of  German  manufacturing  firms,  and  the 
claim  IS  made  that  they  have  to  contend  with  underselhng.  Three  of 
these  estabhshments  are  in  the  vicinity  of  New  York.  The  oldest  and 
largest  is  still  located  in  Buffalo.  It  has  shown  a  commendable 
degree  of  enterprise,  having  taken  out  16  patents  for  new  colors  and 
intermediate  products.  Two  of  its  patented  products  are  manufac- 
tured extensively  in  Germany  imder  Ucense. 

These  firms  have  employed  intermediates,  mostly  from  Germany 
as  the  basis  of  then-  manufacture.     The  works  at  Buffalo  have 
however,  as  already  mentioned,  made  anihne  oil  on  a  large  scale' 
and  have  also  demonstrated  their  abihty  to  manufacture  in  tech- 
nically pure  form  quite  a  group  of  intermediates,  such  as  nitrobenzol 
dmitrobenzol,  nitrotoluol,  dinitrotoluol,  dimethylanihne,  and  a  va- 
riety of  sulphoacids.     Pure  phenol  and  pure  naphthalene  have  also 
*>een  made  in  their  works.     In  all  cases  the  production  has  been 
abandoned  because  German  makers  reduced  their  prices  on  interme- 
diates to  such  an  extent  that  competition  became  hopeless. 

During  the  last  seven  months,  when  it  has  been  almost  impossible  to 
obtain  intermediates  from  Europe,  the  American  works  have  hur- 


V 


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s     '     it 


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nedly  put  up  emergency  plants  and  made  the  requisite  intermediates 
at  considerable  expense  in  order  to  avoid  a  complete  stoppage.  In 
this  connection  material  assistance  has  been  rendered  by  the  intro- 
duction in  1911  of  the  manufacture  of  nitrobenzol  andf  aniline  oil 
and  salts  in  the  works  of  one  of  the  largest  American  companies  en- 
gaged in  the  production  of  chemicals.  This  company  has  been  able 
to  supply  about  one-quarter  of  the  demand  of  American  dyestuff 
manufacturers  for  the  intermediates  in  question. 

The  quality  of  these  compounds  has  been  recognized  as  fully  equal 
to  that  of  European  products,  and  the  abihty  to  make  these  com- 
pounds in  the  United  States  from  American  benzol,  so  hotly  con- 
tested on  the  other  side  of  the  ocean,  has  been  abundantly  demon- 
strated. 

A  plant  is  now  under  erection  that  will  be  able  to  provide  for  one- 
half  of  the  needs  of  the  American  color  makers,  as  far  as  aniline  oil 
and  salts  are  concerned,  and  will  be  capable  of  easy  expansion. 

The  dyes  manufactured  by  the  four  American  estabhshments  are 
chiefly  standard  colors,  called  for  in  fairly  large  quantities,  on  which 
patent  rights  have  expired.  They  number  about  100  and  represent 
the  active  types  in  the  trade.  No  attempt  is  made  to  manufacture 
synthetic  indigo,  which  remams  imder  patent  protection  for  a  few 
years  longer,  or  alizarin,  which  requires  an  exceedingly  expensive 
plant.     Both  of  these  dyestuffs  are  on  the  free  Hst. 

Mention  should  be  made  of  a  fifth  factory  for  makmg  coal-tar  dyes 
which  has  been  estabhshed  m  the  State  of  New  York  by  one  of  the 
largest  German  firms  engaged  in  the  manufacture.  This  branch 
house,  according  to  statements,  is  occupied  with  the  transformation 
of  intermediates  into  finished  dyes,  especially  in  such  cases  where  the 
series  of  operations  is  costly,  and  the  last  steps  relatively  simple  and 
mexpensive.  There  is  manifestly  a  temptation  to  utihze  tariff  pro- 
visions m  this  manner,  and  the  practice  is  probably  not  limited  to 
the  one  foreign  branch.  An  unfinished  dyestuff  pays  10  per  cent 
duty  or  no  duty,  as  compared  with  a  duty  of  30  per  cent  on  the 
finished  product.  The  cost  of  the  last  steps  in  ^'assembling"  the 
finished  dye,  may,  however,  be  less  than  1  per  cent  of  its  total  value. 

Reviewing  the  growth  and  present  status  of  the  manufacture  of 
artificial  dyestuffs  in  the  United  States,  it  may  be  said  that  all  has 
practically  been  accomphshed  that  could  safely  be  attempted  m  the 
face  of  exceptionally  powerful  competition.  Those  conducting  these 
mdustries  have  shown  an  abundant  measure  of  perseverance  and 
patience  in  facmg  economic  difficulties  and  gradually  building  up  as 
extensive  a  structure  as  now  exists.  There  seems  to  be  present  a 
determmation  and  readmess  to  invest  capital  and  energy  on  a  large 
scale  in  expandmg  the  industry  as  soon  as  the  factors  of  safety  are 
assured. 

AMERICAN  SUPPLY  OF  RAW  MATERIALS. 

As  already  noted,  attempts  in  the  past  to  manufacture  intermediates 
have  been  hampered  by  the  insufficiency  of  the  domestic  supply  of 
coal-tar  crudes.  It  is  desirable  at  this  pomt  to  know  exactly  how 
far  the  recovery  of  the  by-products  of  American  gas  works  and  coke 
ovens  IS  developed  and  to  what  extent  they  can  supply  in  the  im- 
paediate  future  the  crudes  needed  by  an  expanded  coal-tar  chemical 
industry.     The  two  sources  of  coal  tar  are  gas  works  and  coke  plants 


24 


DYESTUFFS  FOR  AMERICAN  INDUSTRIES. 


DYESTXJFFS  FOR  AMERICAN  INDUSTRIES. 


25 


•^ 


bi 


COAL  TAR   FROM   GAS   WORKS. 

In  1909,  according  to  the  census  returns,  the  coal  used  in  American 
gas  works  amounted  to  4,941,000  tons,  valued  at  $16,305,000.  At 
the  same  time  580,000,000  gallons  of  oil,  valued  at  $17,346,000,  were 
employed  m  the  production  of  gas.  The  tar  collected  was  92,153,000 
gallons.  Of  this  quantity  78,340,000  gallons,  valued  at  $1,876,000, 
appear  to  have  come  into  the  market.  The  valuation  is  a  little 
over  2  cents  per  gallon.  This  tar  is  not  rich  in  the  hydrocarbons 
benzol,  toluol,  and  xylol,  as  it  is  sought  to  retain  as  large  a  volume 
as  possible  of  these  volatile  constituents  in  the  gas,  in  order  to  in- 
crease the  illuminating  power.  Coal  gas  usually  contains  from  0.5 
to  1.2  per  cent  of  benzol  and  its  homologues.  On  an  average,  when 
coal  is  distilled,  100  pounds  of  coal  yield  1.25  pounds  of  benzol  and 
its  higher  homologues  that  are  present  in  the  gas  evolved.  Of  this 
amount  0.94  pound  is  pure  benzol,  and  0.31  pound  is  toluol  and 
xylol.  A  small  additional  amount  is  found  in  the  tar.  It  consists 
of  0.05  pound  of  benzol,  and  0.08  pound  of  toluol  and  xylol. 

The  coal  tar  from  gas  works  contains  on  an  average  0.32  per  cent 
of  pure  benzol,  0.50  per  cent  of  toluol  and  xyol,  0.26  per  cent  of  pure 
phenol,  4.5  per  cent  of  pure  naphthalene,  and  0.44  per  cent  of  pure 
anthracene. 

Assuming  that  the  present  American  production  of  gas  tar  amounts 
to  100,000,000  gallons,  this  represents  about  1,000,000,000  pounds,  or 
500,000  short  tons.  From  this  quantity  it  is  possible,  on  the  above 
figures,  to  extract:  Benzol,  1,600  tons; toluol  and  xylol,  2,500  tons; 
phenol,  1,300  tons;  naphthalene,  22,500  tons;  antliracene,  2,200  tons; 
and  the  minor  constituents,  cresol,  phenanthrcne,  etc.,  in  proportion. 

COAL  TAR  AND  BENZOL  FROM  COKE  WORKS. 

The  majority  of  the  coke  plants  in  the  United  States  are  equipped 
with  old-fashioned  beehive  ovens,  which  allow  all  gas,  ammonia,  and 
tar  to  be  wasted. 

Modern  recovery  ovens,  with  condensation  plants,  have  been  in- 
stalled to  some  extent  in  this  country.  Their  use  is  much  more 
extended  in  European  coke  works,  especially  in  Germany,  where 
nearly  aU  the  by-products  are  saved.  In  1913  there  were  102,650 
coke  ovens  in  the  tJnited  States,  and  of  these  only  5,688  were  retort, 
or  recovery,  ovens.  The  increase  during  the  year  of  such  ovens  was 
477.  There  was  a  decrease  in  the  number  of  beehive  ovens  of  57. 
At  the  close  of  the  year  504  retort  ovens  were  under  construction,  and 
contracts  had  been  made  for  building  many  more.  During  1913, 
30,485  beehive  ovens— 31.4  per  cent  of  the  entire  number— were  idle 
throughout  the  entire  year. 

In  1912  the  amount  of  coal  used  for  coke  plants  reached  65,578000, 
short  tons.  The  coke  produced  totaled  32,869,000  tons,  valued  at 
$69,172,000,  from  beehive  ovens,  and  11,115,000  tons,  valued  at 
$42,633,000,  from  recovery  ovens;  in  all,  43,984,000  tons,  valued  at 
$111,805,000.  The  coke  obtained  from  the  recovery  ovens  repre- 
sents 25  per  cent  of  the  total  product  in  quantity  and  38  per  cent  in 
value. 

The  retort  ovens  are  expensive,  but  the  increased  outlay  is  more 
than  compensated  by  the  value  of  the  ammonia,  tar,  and  gas  recov- 


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ered,  especially  if  there  is  an  adequate  demand  at  hand  for  the  gas. 
The  recovery  plants  contain  the  necessary  condensers  for  collecting 
ammonia  and  tar,  but  are  not  always  provided  with  the  ''scrubbers," 
or  benzol  towers,  designed  to  extract  from  the  otherwise  purified  gas 
the  benzol  and  toluol  present  therein  and  enhancing  the  value  for 
illuminating  purposes. 

In  the  towers  the  current  of  gas  comes  in  contact  with  the  heavier 
oils  obtained  in  the  distillation  of  coal  tar,  and  the  benzol  and  toluol 
present  are  largely  absorbed  by  them.  The  oils,  when  saturated,  are 
i*un  into  a  still,  and  the  benzol  and  toluol  are  driven  out  by  heat  and 
are  collected  in  suitable  condensers.  Benzol  towers  constitute  an 
important  additional  item  of  expense,  and  introduce  an  additional 
complication  into  the  general  process.  They  give  a  yield  of  about 
22  poimds  of  benzol  and  toluol  for  each  ton  of  coal  submitted  to 
coking.  Their  construction  has  hitherto  been  largely  dependent 
upon  the  current  demand  for  these  hydrocarbons.  The  cost  of  benzol 
towers  for  a  plant  coking  300  tons  of  coal  daily  is  about  $21,000  in 
Germany.  It  requires  a  capital  of  about  $5,000  for  operation.  The 
operating  expenses  are  about  $23,000  per  annum.  Such  a  plant 
gives  yearlv  profits  exceeding  $30,000  when  benzol  prices  are  favor- 
able. With  low  prices  for  benzol  it  may  barely  meet  the  cost  of 
operation.  The  65,000,000  tons  of  coal  now  employed  in  coking  are 
capable  of  producing  715,000  tons  of  benzol  and  its  nomologues  from 
benzol  towers  alone,  but  the  cost  of  the  necessary  plant  would  be 
over  $14,000,000. 

It  is  estimated  that  our  present  system  of  coking  involves  an  annual 
loss  of  $75,000,000,  but  at  the  present  rate  of  advance,  by  1920  one- 
half  of  our  coke  supply  wiU  come  from  recovery  ovens.  The  intro- 
duction of  such  ovens  in  the  United  States  began  in  1892. 

The  tar  recovered  in  American  coke  plants  was  66,300,000  gallons 
m  1910.  It  rose  to  94,300,000  gallons  in  1912,  with  a  value  of 
$2,311,000,  or  2.45  cents  per  gallon.  The  weight  of  this  tar  was 
about  944,000  tons.  Taking  as  a  basis  the  customary  yield  obtained 
from  coke  tar,  this  contains  16,420  tons  of  benzol,  toluol,  etc.;  2,380 
tons  of  phenol;  56,600  tons  of  naphthalene;  and  1,890  tons  of 
anthracene,  and  the  minor  constituents  in  proportion. 

From  the  65,000,000  tons  of  coal  now  used  in  coking  it  would, 
however,  be  possible,  with  complete  recovery  plants,  to  obtain 
3,350,000  tons  of  tar,  or  three  and  one-half  times  the  present  quantity. 
This  would  mean  a  potential  supply  from  the  tar  of  coke  plants,  on  an 
existing  basis  of  production,  of  approximately  58,000  tons  of  benzol, 
toluol,  etc.;  8,300  tons  of  phenol;  200,000  tons  of  naphthalene;  and 
6,700  tons  of  anthracene. 

Together,  the  existing  gas  and  coke  production,  provided  the  latter 
be  completely  equipped  with  recovery  plants,  can  furnish  tar  and 
benzol  capable  of  yielding  annually  approximately  780,000  tons  of 
benzol;  9,600  tons  of  phenol;  222,000  tons  of  naphthalene;  and  9,000 
tons  of  anthracene;  and  the  minor  compounds,  cresol,  methyl,  an- 
thracene, phenanthrene,  and  carbazol  in  the  customary  relative  pro- 
portions. 

From  existing  American  gas  works  and  coke  plants,  as  equipped 
at  present,  about  25,000  tons  annually  of  benzol,  toluol,  and  xylol 
can  be  obtained  if  there  is  sufficient  demand,  and  the  proportionate 
quantities  of  the  other  constituents. 


26 


if 


DYESTUFFS  FOR  AMERICAN  INDUSTRIES. 


These  figures  for  the  possible  and  potential  production  in  the 
United  States  of  the  crude  coal-tar  proaucts  may  De  compared  with 
those  for  the  production  in  Germany. 

In  1910  Germany  was  equipped  to  produce,  if  necessary,  98,000 
metric  tons  of  benzol  and  its  homologues  (metric  ton  =  2,204.6 
pounds).  The  actual  production  was  66,000  tons.  Of  this,  56,000 
tons  were  benzol  and  10,000  tons  toluol  and  higher  homologues.  A 
little  over  one-half  of  the  total  product  was  sold  for  use  in  motors, 
automobiles,  etc.  Aniline  color  works  required  32,300  tons.  As  Ger- 
many supplies  over  two-thirds  of  the  finished  coal-tar  dyes  now  pro- 
duced, and  the  ^eat  bulk  of  the  intermediates  required  in  other 
countries,  fumishmg  from  German  works  nearly  all  of  the  crudes,  it 
is  evident  that  the  United  States  has  at  hand  the  raw  material  requi- 
site for  supplying  the  crudes  needed  in  the  manufacture  of  over  one- 
half  the  world's  supplv  of  artificial  dyestuffs.  At  the  same  time  its 
coke  industry  is  capable,  upon  demand,  of  furnishing  in  the  future 
twenty  times  as  much  benzol,  etc.,  as  the  world  now  requires  for 
coal-tar  colors. 

PRESENT  PRODUCTION  OF  CRUDE  TAR  PRODUCTS. 

The  handling  of  coal  tar  and  its  further  treatment  are  concentrated 
in  a  few  hands,  as  is  the  case  in  Germany.  This  has  given  to  the 
industry  a  pronounced  unity  and  economy.  Consumers  of  coal-tar 
crudes  state  that  there  has  been  a  marked  disposition  to  meet  their 
needs,  and  to  so  adapt  and  modify  manufacturing  processes  that 
domestic  demands  may  be  met  as  far  as  general  market  conditions 
permit. 

In  1911  the  amoimt  of  coal  tar  subjected  to  distillation  amounted 
to  56,000,000  gallons.  The  remainder  of  the  tar  production  was 
employed  in  the  manufacture  of  roofing  paper  ana  for  sprinkling 
streets.  There  is  not  much  attempt  to  obtam  separate  products  in 
a  state  of  purity.  The  most  important  products  are  the  light  oil, 
creosote  oil,  and  the  residual  pitch.  Tnese  articles  can  compete 
successfully  with  European  products.  The  light  oil,  containing  ben- 
zol, etc.,  constitutes  about  1  per  cent  of  the  tar.  It  is  used  largely 
for  a  solvent,  for  cleaning  purposes,  and  as  an  iUuminant.  The 
creosote  oil  constitutes  about  23  per  cent  of  the  tar  and  is  used  exten- 
sively for  preserving  timber.  The  domestic  supply  is  far  from  cover- 
ing tne  current  demand. 

In  1914  the  United  States  imported  61,000,000  gallons  of  creosote 
oil,  valued  at  $3,840,000,  Great  Britain  supphed  41,000,000  gallons, 
Germany  10,000,000,  and  the  remainder  came  largely  from  Belgium 
and  the  Netherlands.  The  home  production  of  creosote  oil  in  1909 
was  13,000,000  gallons.     It  has  about  doubled  since  then. 

With  regard  to  the  production  in  the  United  States  of  the  coai-tar 
crudes,  necessary  for  dyestuff  manufacture,  the  following  is  the 
situation: 

Benzol,  toluol^  xylol. — Such  limited  amoimts  as  have  been  called 
for  to  make  intermediates  in  American  works,  about  500  tons  annually, 
have  been  supplied  the  last  few  years.  Provision  can  be  quickly 
made  for  an  ample  supply  on  a  much  more  extensive  scale  if  a  per- 
manent demand  is  evident. 


DYESTUFFS  FOR  AMERICAN  INDUSTRIES. 


27 


Phenol,  or  carbolic  add, — The  method  of  treating  American  coals 
IS  such  as  to  favor  a  relatively  low  production  of  phenol  in  coal  tar. 
There  has  been  httle  attempt  to  separate,  regularly,  technically  pure 
>  phenol  from  the  tar  distillates. 

The  American  demand  is  covered  mostly  by  importations  from 
abroad.     In  1913  American  imports  were  valued  at  $675,000.     Of 
the  import  of  4,077  tons,  Germany  supphed  1,354  tons.  Great  Britain 
2,422  tons,  and  the  Netherlands  287  tons.     The  average  price  was 
^  $166  per  short  ton.     In  addition  to  furnishing  material  ?or  a  variety 

i  of  important  dyes,  phenol  has  an  extended  use  in  medicine,  in  the  man- 

ufacture of  explosives,  and  in  various  industries.     One  important 
chemical  made  from  phenol  is  sahcylic  acid,  widely  used  in  medicine 
as  well  as  in  the  manufacture  of  artificial  dyes.     This  is  imported  to 
^  the   extent  of  32,000   pounds.     Another  derivative  is  picric   acid 

used  as  an  explosive  as  well  as  a  dye.     The  import  is  now  85  000 
pounds,  valued  at  $18,000.  ' 

The  embargo  on  exports  of  phenol  from  Europe  during  the  last  few 
months,  on  account  of  its  importance  in  connection  with  military 
4  supphes^  has  forced  American  chemists  to  fall  back  on  its  synthetic 

production  from  benzol.  The  operation  is  relatively  easy.  It  is 
based  upon  the  transformation  of  benzol  mto  its  sulphonic  acid  by  the 
action  of  sulphuric  acid,  and  the  fusion  of  the  product  with  caustic 
soda.  With  an  ample  supply  of  benzol  the  manufacture  of  synthetic 
I  phenol  in  the  United  States  could  be  readily  assured,  at  a  cost  not 

much  in  advance  of  that  of  the  European  product. 

NaphtJialene.— This  is  a  leading  constituent  of  coal  tar  and  fur- 
nishes a  variety  of  derivatives  employed  in  dye  manufacture.     The 
bulk  of  the  pure  product  is  used  as  a  moth  preventive.     The  United 
t  States  consumes  annually  about  5,000  short  tons.     Nearly  1,600  tons 

^  are  supphed  by  American  tar  distillers.     The  remainder  comes  from 

Germany  and  Great  Britain,  in  about  equal  amounts.  Phthalic  acid, 
one  of  the  most  important  derivitives  of  naphthalene,  is  imported  to 
the  extent  of  38  tons  annually,  with  a  value  of  $21,000.  Naphtha- 
lene is  a  proniinent  constituent  of  the  fraction  of  creosote  oil  ob- 
f  tained  in  the  distillation  of  coal  tar.     It  is  a  purely  commercial  ques- 

tion to  the  tar  distiller,  whether  he  can  more  profitably  sell  the  crude 
creosote  oil  or  separate  out  the  naphthalene  present  therein. 

Anthracene.— This  hydrocarbon  is  also  present  in  the  creosote  oil, 
and  the  same  question  arises  as  to  the  profit  of  its  separation.     No 
K  attempt  is  niade  in  American  tar  works  to  isolate  this  valuable  con- 

stituent, which  serves  as  the  basis  of  the  manufacture  of  synthetic 
•  ahzarin  and  all  the  alizarin  dyestuffs. 

The  same  may  be  said  of  the  relatively  small  but  still  important 
amounts  of  cresol,  methylanthracene,  phenanthrene,  and  carbazol, 
all  of  which  occur  in  the  creosote  oil,  and  all  of  which  are  essential  to 
an  mdustry  providing  all  current  artificial  dyestuffs.  It  should  be 
mentioned  here  that  the  quantity  of  anthracene  present  in  the  coal 
tar  now  treated  in  American  tar  works  is  far  in  excess  of  that  required 
to  manufacture  the  alizarin  dyes  imported  into  the  United  States, 
while  the  naphthalene  present  could  more  than  meet  the  demands  of 
the  world's  entire  dyestuff  manufacture. 

A  competent  authority  gives  the  following  estimate  for  products 
of  the  coal-tar  industry  in  the  United  States  for  1914:    Total  pro- 


28 


DYESTTJFFS  FOR  AMERICAN  INDUSTRIES. 


DYESTUFFS   FOR  AMERICAN   INDUSTRIES. 


29 


N 


duction  of  refined  benzol  in  all  forms,  2,550,000  gallons,  or  about 
9,600  short  tons  (of  this  amount,  200,000  gallons,  or  750  tons,  was 
devoted  to  the  manufacture  of  aniline  compounds) ;  total  production 
of  refined  toluol,  in  all  forms,  840,000  gallons,  or  about  3,200  tons 
(nearly  all  used  for  making  explosives) ;  production  of  refined  phenol, 
75  tons;  production  of  refined  naphthalene,  1,500  tons. 

PRICE   MOVEMENT   OF   AMERICAN   COAL-TAR   CRUDES. 

Since  August  1,  1914,  there  has  been  a  steady  movement  upward 
in  the  market  rates  for  nearly  all  crude  products  of  coal  tar,  required 
in  making  dyestuffs  or  explosives.  The  following  table  shows  the 
increases : 


Crudes. 


Benzol  : 

f*ure per  gallon . 

100  per  cent do. 

90  per  cent do. . . 

50  per  cent do 

Toluol: 

I'ure do... 

Commercial do. . . 

Xylol ,  pure do . . . 

Solvent  naphtha do. . . 

Heavy  naphtha do .  [ . 

Naphthalene,  pure i)or  pound. 

Phenol ,  pure do . . . 


Aug.l, 

Feb.  15, 

1914. 

1915. 

90.30 

SO.  40 

.27 

.37 

.25 

.35 

.28 

.38 

.35 

.45 

.27 

.40 

1.20 

1.20 

.27 

.27 

.18 

.16 

.023 

.033 

.075 

1.00 

The  present  quotation  for  phenol  is  nominal.  The  demand  for 
phenol  is  so  far  in  excess  of  the  supply,  foreign  or  domestic,  that 
exaggerated  prices  are  often  offered  without  finding  any  taker. 
American  toluol  is  used  almost  entirely  for  producmg  high  explosives. 
The  naphthas,  mixtures  of  the  hydrocarbons,  not  used  for  dyestuffs, 
etc.,  show  no  tendency  to  rise. 

POSITION   OF   THE   AMERICAN   TAR   DISTILLER. 

The  tar  industry  of  the  United  States  is  on  a  different  basis  from 
that  of  Europe.  In  Europe  its  importance  is  confined  almost  en- 
tirely to  the  production  of  raw  material  for  a  highly  organized 
chemical  industry.  Here  the  use  of  tar  itself  is  widespread,  wnile  the 
utilization  of  its  chief  constituent,  pitch,  is  confined  to  very  narrow 
limits  across  the  ocean.  Pitch  forms  70  per  cent  of  coal  tar.  In 
Germanv  little  use  is  made  of  it  except  as  a  fuel.  Nine-tenths  of 
the  pitch  supphed  by  American  tar  works  is  employed  in  road  mak- 
ing, in  roofing,  and  in  general  waterproofing. 

The  very  extended  use  of  creosote  oil  in  the  United  States  makes 
it  a  purely  commercial  question  as  to  whether  the  tar  distiller  should 
attempt  a  refining  of  its  constituents.  The  current  demand  in 
America  for  benzol,  toluol,  and  xylol  is  entirely  met  by  the  product 
from  the  benzol  towers  of  coke  plants. 

To  attempt  any  extended  provision  for  supplying  the  entire  range 
of  coal-tar  crudes,  such  as  might  be  required  m  the  United  States 
for  the  manufacture  of  its  own  supply  of  artificial  dyestuffs,  would 
mean  an  assurance  that  the  distiller  could  profitably  dispose  of 
nearly  all  of  the  products  isolated  in  a  more  or  less  pure  form  during 


f 


\ 


t    ■  • 


i    1^ 


the  various  processes,  and  secured  in  far  different  proportions  from 
those  required  in  the  general  manufacture  of  coal-tar  dyestuffs.  At 
once  he  would  face  a  very  delicate  and  compUcated  problem,  with 
many  factors,  technical,  economic,  financial.  A  dominant  factor  is 
an  assured  market,  if  he  enlarges  his  plant  on  a  scale  comparable  with 
foreign  establishments. 

Less  than  10  per  cent  of  tar  consists  of  matters  available  for  use  in 
the  dyestuff  industry.  If  a  distiller  attempts  to  meet  the  needs  of  a 
growing  or  rapidly  expanded  domestic  dyestuff  industry,  he  must 
find  channels  for  d.isposing  of  the  remaining  90  per  cent. 

The  tar  distiller  feels  that  he  should  not  be  expected  to  embark  in 
the  manufacture  of  intermediates,  but  that  this  branch  should  be 
undertaken  preferably  by  the  producer  of  heavy  chemicals,  as  the 
production  of  intermediates  means  a  heavy  consumption  of  acids, 
alkalies,  and  a  variety  of  other  chemicals. 

There  seems  to  be  no  lack  of  enterprise  in  the  tar-distilling  branch; 
but  there  does  seem  to  be  a  deep-seated  conviction  that  fundamental 
changes  in  legislation  are  absolutely  essential  before  any  far-reaching 
effort  can  be  organized,  to  assure  the  preparation  from  American 
coal  tar  of  an  adequate  supply  of  ''crudes  for  the  needs  of  a  self- 
contained  American  coal-tar  dyestuff  industry. 

SUPPLY   OF   GENERAL   CHEMICALS   REQUIRED. 

With  regard  to  the  great  bulk  of  the  heavy  chemicals  required  in 
the  coal-tar  dyestuff  industry,  the  United  States  is  now  compara- 
tively independent  of  the  rest  of  the  world.  This  is  especially  the 
case  with  sulphuric  acid,  hydrochloric  acid,  sodium  carbonate, 
caustic  soda,  wood  alcohol,  grain  alcohol,  and  the  chromates,  all 
of  which  are  used  in  large  amounts.  Liquid  chlorine  can  easily  be 
produced  here  on  a  large  scale  by  electrolytic  methods  if  the  demand 
exists.  The  same  can  be  said  of  glacial  acetic  acid  and  of  acetic 
anhydride,  the  raw  material  for  which  is  furnished  abundantly  by 
numerous  plants  for  wood  distillation.  In  common  with  the  rest 
of  the  world,  the  United  States  depends  largely  upon  Germany  for 
potash  compounds.  The  world  depends  likewise  upon  Chile  for  the 
raw  material  required  in  making  nitric  acid  and  sodium  nitrite, 
except  as  these  products  are  ob tamed  from  the  air  by  the  new  pro- 
cesses for  oxidizing  atmospheric  nitrogen.  There  is  promise  of  this 
new  industry  being  created  in  the  United  States.  For  the  time  being 
Norway,  with  its  very  cheap  water  power  for  generating  electricity^ 
is  the  only  country  where  the  synthetic  production  of  nitric  acid  is  a 
pronounced  success  on  a  fairly  large  scale.  Most  of  the  nitrite 
required  for  the  manufacture  of  coal-tar  dyestuffs  is  very  advan- 
tageously manufactured  as  an  adjunct  of  the  Norwegian  nitric-acid 
production.  The  bulk  of  the  nitric  acid  made  in  Norway  is  transformed 
immediately  into  nitrates  for  use  as  fertihzer.  All  of  Norway's  water 
power,  if  utilized  for  the  production  of  nitric  acid  and  nitrates, 
would  suffice  for  the  production  of  only  a  fraction  of  the  world's 
demands.  In  this  connection  it  is  of  interest  to  note  that  Germany 
has  hastily  erected  works  on  the  Rhine  for  the  production  of  nitric 
acid  from  atmospheric  nitrogen,  generating  the  necessary  electric 
current  at  high  cost  by  means  of  coal.  The  works  will  be  in  operation 
by  April,  1915,  and  will  partly  meet  the  vastly  increased  demand  for 
mtric  acid  required  in  the  manufacture  of  explosives. 


30 


DYESTUFFS  FOR  AMERICAN   INDUSTRIES. 


DYESTUFFS  FOR  AMERICAN  INDUSTRIES. 


31 


1 


THE  GERMAN  COAL-TAR  DYESTUFF  INDUSTRY. 

As  already  noted,  all  efforts  to  build  up  on  a  large  scale  a  distinctly 
American  coal-tar  chemical  industry  have  been  crippled  and  rendered 
useless  when  brought  into  conflict  with  the  interests  of  the  German 
coal-tar  chemical  industry.  It  is  necessary  to  analyze  the  sources  of 
this  power,  exerted  apparently  with  such  ease  in  all  the  leading  indus- 
trial countries  of  the  world,  but  felt  most  keenly  in  the  United  States, 
with  its  abundant  supply  of  the  raw  materials  and  its  large  and  rapidly 
growing  consumption  oi  artificial  dyestuffs. 

First  of  all,  it  is  important  to  establish  just  how  large  a  proportion 
of  the  world's  production  of  artificial  ayes  is  made  in  Germany. 
From  export  returns  and  careful  estimates  of  local  consumption,  the 
following  may  be  regarded  as  a  fairly  approximate  statement  of  the 
world's  present  production  of  finished  coal-tar  dyes: 


Countries. 


Germany 

Switzerland.. 
Great  Britain . 

France 

United  States 
Austria 


Value. 


$68,300,000 
6, 450, 000 
6,000,000 
5,000,000 
3,000,000 
1,500,000 


Countries. 


Russia 

Beleium 

Netherlands . . . 
Other  countries 

Total 


Value. 


11,000,000 
500,000 
200,000 
200,000 


92,150,000 


This  shows  that  Germany  furnishes  74  per  cent,  or  about  three- 
quarters,  of  the  world's  dyes. 

The  production  of  artificial  dj^estuffs  for  exportation  is  confined 
practically  to  Germany,  Great  Britain,  and  Switzerland.  The  values 
of  such  exports  in  1912  were:  Germany,  $48,430,000,  or  88.2  per 
cent;  Switzerland,  $5,450,000,  or  9.9  per  cent;  Great  Britain, 
$990,000,  or  1.8  per  cent;  total  value,  $54,870,000.  In  the  world's 
markets  Germany's  domination  is  evident,  Switzerland  being  prac- 
tically the  only  competitor. 

The  distribution  oi  Germany's  exports  of  artificial  dyestuffs  amons 
the  different  countries  is  a  matter  of  interest.  The  exports  of  finished 
dves  in  1912  were  valued  as  follows:  Aniline  dyes,  $31,836,000; 
alizarin,  $2,197,000;  anthracene  dyes,  $3,429,000;  indigo,  $10,968,000; 
total,  $48,430,000.  The  following  table,  compiled  by  Dr.  Bernhard 
C.  Hesse,  the  well-known  chemist  and  statistician,  shows  very  clearly 
the  present  dependence  of  the  various  countries  upon  Germany  for 
their  supplies  and  the  importance  of  the  United  States  as  the  leading 
customer.  Noteworthy  is  the  enormous  consumption  of  synthetic 
indigo  by  China.  The  table  shows  the  percentage  of  the  exports  of 
each  dye  taken  by  the  principal  consimiers. 


Consuming  countries. 

Aniline 
dyes. 

Alizarin. 

Anthra- 
cene 
dyes. 

Indigo. 

Europe: 

Great  Britain 

Per  cent. 

17.14 

2.15 

.65 

1.03 

6.38 

8.99 

.68 

.35 

.lA 

Per  cent. 

24.34 

1.59 

Percent. 

23.72 

2.52 

Per  cent. 
3.54 

France 

.97 

Portueal 

Spain..                           

.20 

Italy 

3.23 
6.80 

1.96 

Austria 

3.38 

4.08 

Turkey     .                                

.33 

Roumania 

Servia 

I 


Constuning  coiutries. 

Aniline 
dyes. 

Alizarin. 

Anthra- 
cene 
dyes. 

Indigo. 

Europe— Continued. 

RnliniriA .    

Per  cent. 

.20 

.10 

1.22 

1.71 

.37 

.42 

1.40 

.37 

2:12 

3.90 

5.45 
13.17 

5.35 
.22 
.38 

Per  cent. 

Per  cent. 

Per  cent. 

Greece .... 

RwitziPrl^nd , 

4.23 
2.83 

Russia 

3.17 

1.30 

Finland 

Norway. 

Sweden . 

.73 

Denmark.... 

.08 

Netherlands. 

3.09 

2.76 
L96 

1.63 

1.83 

Belrium. ...... .         . 

.94 

Asia: 

Japan 

2.46 

China 

64.03 

British  India 

39.89 

4.44 

.97 

British  Malacca 

.36 

Dutch  East  Indies 

8.41 

L49 

2.86 

Persia 

.18 

South  America: 

Areentina. 

.25 
.98 
.09 

.69 
21.55 

.85 

.34 
.16 

, 

Brazil 

Chile 

North  America: 

Canada 

.25 

United  States 

&03 

44.10 

lass 

Mexico 

.05 

Africa: 

Ecvpt 

L33 

Australia: 

Australian  coloni<^r 

.47 

Recapitulation: 

Europe 

49.32 

24.57 

1.32 

23.09 

.34 

.16 

39.46 
48.30 

44.89 
7.56 

15.20 

Asia 

7a  86 

South  America 

Nwth  America 

8.03 

44.10 

ia68 

Africa 

1.33 

Australia 

.47 

•          •  .      . 

Total 

98.80 

95.79 

96.55 

98.54 

TRADE  IN   CRUDES  AND  INTERMEDIATES. 

The  domination  of  the  German  color  industry  is,  however,  greater 
than  would  appear  from  the  export  statistics  for  finished  dyes.  As 
far  as  the  production  of  crude  coal-tar  products  is  concerned,  Ger- 
many has  been  for  nearly  20  years  practically  independent  of  other 
countries.  Its  own  tar  industry  produces,  or  is  capable  of  producing, 
all  crude  compounds  needed  in  tne  industry.  The  nearest  approacn 
to  an  exception  is  in  the  case  of  anthracene,  the  raw  material  for  the 
manufacture  of  alizarin  and  an  important  class  of  dyes.  There  is 
enough  of  this  hydrocarbon  in  German  tar  to  meet  the  needs  of  the 
dyestuff  works.  In  England,  however,  the  separation  of  anthracene 
from  the  heavv  oil  of  the  tar  works  has  been  highly  perfected  and  it 
is  commercially  profitable  to  draw  upon  the  Englisn  supply.  The 
independence  otherwise  of  the  German  production  of  cruaes,  and  its 
ability  to  send  supphes  to  other  countries,  is  shown  by  the  following 
summary,  for  1912,  of  Germany's  trade  in  crude  coal-tar  products: 


Crudes. 

Imports. 

Exports. 

Benzol  and  bomologues 

S509,000 

537,000 

7,600 

184,000 

66,400 

$1,631,000 

852  000 

Phenol 

Cresol 

72,C01 
211  003 

Naphthalene 

Anuracene 

12  noo 

Total 

1,304,000 

2,778,000 

86201*»— 16- 


32 


DYESTUFFS  FOR  AMERICAN   INDUSTRIES. 


I 

i 


Germany's  excess  of  exports  is  $1,474,000. 

Much  more  striking  and  of  far-reaching  importance  is  the  revela- 
tion of  the  figures  contained  in  the  summary,  for  1912,  of  Germany's 
trade  in  intermediate  coal-tar  products: 


Aniline  oil  and  salt 

Naphthol,  and  naphthalene  compounds 

Nitrobenzol,  resorcin,  phthalic  acid,  anthraquinone,  etc 

Total 


152,000 


$1,559,000 

682,000 

1,433,000 


3,674,000 


Here  is  an  excess  of  $3,522,000  in  favor  of  the  exports.  A  calcu- 
lation based  upon  the  unit  prices  of  the  various  coal-tar  products 
shows  that  in  a  rough  approximate  way  crudes  worth  $1  produce 
intermediates  worth  $3.56  and  finished  dyes  worth  $7.61.  Assum- 
ing that  one-half  of  the  excess  of  exports  of  crudes  and  all  of  the 
excess  of  intermediates  are  used  to  produce  colors  in  other  coun- 
tries, the  value  of  the  dyes  manufactured  abroad  from  German 
products  would  be,  from  crudes,  $5,608,000;  from  intermediates, 
$7,529,000;  total,  $13,137,000. 

These  figures  show  how  largely  the  manufacture  of  dyes  outside 
of  Germany  depends  upon  the  industries  of  that  Empire  for  the 
primary  and  intermediate  compounds  serving  as  raw  materials. 
The  manufacture  of  artificial  dyestuffs  outside  of  Germany  has 
a  value  of  about  $24,000,000,  and  over  one-half  is  made  with  mate- 
rials from  German  factories. 

The  effects  of  this  condition  are  seen  in  the  trade  statistics  of 
other  countries.  Switzerland's  net  excess  of  crudes  imported  is 
$315,000;  of  intermediates,  $846,000.  Austria  exports  a  net  excess 
of  3,309  metric  tons  of  crudes,  and  the  net  excess  of  imported  inter- 
mediates is  1,032  tons.  Great  Britain  exports  crudes  worth  $2, 073, 000, 
and  intermediates  worth  $156,000.  British  imports  of  both  classes — 
but  chiefly  intermediates — are  valued  at  $758,000. 

As  already  noted,  nearly  all  the  intermediates  employed  in  manu- 
facturing coal-tar  dyestuffs  in  the  United  States  come  from  Germany. 
This  is  also  the  case  for  Belgium,  the  Netherlands,  and  Russia,  and 
very  largely  so  for  France. 

Briefly  stated,  Germany  makes  three-quarters  of  the  world's  arti- 
ficial dyes  and  controls  the  supply  of  raw  material  for  one-half  of  the 
remainmg  quarter.  Furthermore,  for  one  great  class  of  dyes,  the  aliza- 
rin colors,  and  for  a  vast  number  of  minor  subdivisions,  that  country 
is  almost  the  sole  source  of  supplv.  It  possesses  in  an  exceptional 
degree  a  well-known  commercial  power  to  influence  if  not  force 
customers  requiring  a  large  variety  of  dyestuffs  to  purchase  from  it 
all  the  entire  stock  needed.  The  industry  is  in  such  a  position  that  it 
can  easily  render  almost  impossible  in  a  given  country  the  production 
of  intermediates  or  finishea  dyes,  unless  prevented  by  governmental 
protection  or  assistance. 

The  exceptional  position  of  the  Swiss  industry  is  due  to  the  fact 
that  it  started  simultaneously  with  the  German  industry,  and  kept 
even  step  with  its  more  powerful  neighbor  in  the  different  stages  of 
evolution.    There  are  very  friendly  relations  between  the  leaders  in 


DYESTUFFS   FOR  AMERICAN   INDUSTRIES. 


33 


/ 1 


I 


\ 


ri 


the  two  coimtries.  The  bulk  of  the  Swiss  production  is  at  Basel, 
on  the  German  frontier.  The  Swiss  industry  depends  chiefly  on 
Germanvfor  its  intermediates  and  for  its  heavy  chemicals;  at  the  same 
time  it  does  not  threaten  the  supremacy  of  the  German  dyestuff  trade 
in  the  world's  markets. 

CAUSES  OF  GERMANY'S  SUPREMACY. 

The  actual  supremacy  of  Germany  in  the  production  of  coal-tar 
dyes  has  been  outlined  above  and  its  dominating  position  in  inter- 
national commerce  clearly  shown.  It  remains  to  describe  how  this 
supremacy  has  been  won  and  how  it  is  maintained. 

The  base  of  the  present  structure  was  laid  half  a  century  ago 
when  the  industrv  of  artificial  dyestuffs  was  still  in  swaddling 
clothes.  A  remarkable  number  of  German  chemists  of  the  first 
rank  and  of  the  second  rank  were  attracted  to  the  new  industry. 
The  admirably  equipped  laboratories  of  the  German  imiversities  and 
schools  of  science  were  devoted  largely  to  research  in  the  new  field. 
Simultaneously,  in  Germany,  the  molecular  constitution  of  the  aro- 
matic hydrocarbons  was  revealed  by  Kekul6,  and  a  vast  amoimt  of 
scientific  knowledge,  keen  mental  effort,  high  inventive  capacity,  and 
patient  labor  was  devoted  to  applying  the  new  theories  to  the  dis- 
covery of  tinctorial  compoimds  among  the  derivatives  of  the  aro- 
matic series.  A  small  army  of  plodding,  but  still  clever,  young 
chemists  carried  out  thousands  and  thousands  of  separate  researches 
under  the  leadership  of  brilliant  men,  such  as  Hoffmann;  Bayer, 
Liebermann,  Graebe,  Witt,  and  many  others.  Far  more  was  done  in 
Germany  to  develop  the  possibilities  in  the  province  of  synthetic 
dyes  than  in  all  the  rest  of  the  world.  At  the  same  time  the  young 
industry  was  fortunate  in  securii^  the  generous  cooperation  of  finan- 
ciers with  farsighted  courage  and  technical  managers  of  exceptional 
sagacity.  What  is  said  of  Germany  is  also  essentially  true  of  Swit- 
zerland but  naturally  on  a  more  modest  scale.  The  seventies  saw 
the  industry  well  defined  and  established  upon  a  solid  basis,  while 
the  progress  of  discovery  continued  at  an  increased  rate.  The 
notable  triumph  of  this  period  was  the  introduction  of  synthetic 
alizarin.  Durmg  the  eighties  there  was  an  increased  appearance  of 
new  classes  of  important  dyes.  It  was  the  golden  decade.  The 
mdustry  was  recognized  as  one  of  the  great  national  assets  of  Ger- 
many. In  the  nineties  there  was  a  decided  lull  in  invention.  Great 
attention  was  devoted  to  the  standardizing  of  manufacture,  and  espe- 
cially to  the  organization  of  the  foreign  trade.  Germany  became 
practically  independent  of  the  world  in  regard  to  its  supply  of  coal- 
tar  crudes.  The  relations  between  the  great  manufacturing  houses 
became  cordial,  and  there  was  a  general  spirit  of  cooperation.  The 
manufacture  of  a  large  number  of  valuable  medicinals  and  photo- 
graphic chemicals  from  coal-tar  intermediates  was  added  to  the  pro- 
duction of  dyestuffs.  Great  quantities  of  these  intermediates  were 
•u  ^"°^^^y®^  ^  ^^^  preparation  of  high  explosives.  All  this  con- 
tributed to  making  the  mdustry  better  balanced  and  more  symmetric, 
whde,  of  course,  adding  to  its  complexity. 

The  present  century  has  seen  a  steady  development.  Synthetic 
mdiffo  won  its  great  victory.  The  discovery  of  new  types  of  colors 
has  become  rare.    Close  trade  agreements  have  come  into  existence, 


* 
^ 


K\' 


S4 


DYESTUFFS  FOR  AMERICAN  INDUSTRIES. 


I 


With  Government  approval,  and  have  been  maintained  without 
difliculty.  At  present  the  mdustry  is  the  most  remunerative  in  the 
J^mpire,  and  the  one  most  conspicuous  in  international  trade  as 
distmctly  and  predonunantly  German.  It  has  been  created  in 
Germany,  and  is  regarded  by  Germans  as  then-  most  briUiant  triumph 
m  applying  science  to  industry.  The  rest  of  the  worid  generously 
recognizes  the  full  right  of  Germany  to  be  justly  proud  of  its  accom- 
phshment. 

RESEARCH  THE   CHIEF  CAUSE. 

Unquestionably  the  chief  factor  in  favoring  the  early  start  of  the 
industry  and  its  remarkably  rapid  and  harmonious  development 
was  the  spirit  of  research  in  Germany  and  the  marvellous  equipment 
for  facihtatmg,  largely  at  pubhc  expense,  the  exercise  of  this  spuit 
While  other  countnes  sought  to  encourage  the  introduction  of^new 
branches  of  mdustry  by  the  aid  of  tanff  protection,  in  Germany 
manufacturers,  capitahsts,  and  Government  officials  ^arly  recognized 
the  creative  power  and  earning  capacity  of  highly  organized  industrial 
research.  Any  marked  advance  m  developing  the  coal-tar  chemical 
mdustry  m  the  Umted  States  must  depend  upon  the  full  recognition 
of  this  fact,  for  no  other  industry  is  so  intimately  associated  with 
research  of  the  highest  scientific  character. 

A  most  competent  authority.  Dr.  B.  C.  Hesse,  says  in  this  connec- 
tion: 

What  we  do  need  is  a  semimanufactiiring  laboratory  in  which  to  ascertain  the  most 
favorable  conditions  for  carrying  out  those  operations  which  the  work  of  the  Germans 
both  in  their  patents  and  in  their  commercial  exploitation  of  them,  has  shown  to  be 
needful  or  worthy  of  prosecution.  That,  however,  is  no  child's  play  task;  it  calls  for 
engineering  skill  of  the  hidiest  order  chemical  knowledge  of  great  refinment,  and 
experimental  ability  of  high  rank.  Much  will  have  to  be  learned  and  determined  as 
to  the  proper  materials  of  construction,  the  proper  size  and  shape  of  the  apparatus  and 
the  most  favorable  working  unit,  which  is  by  no  means  constant  from  one  dyestuff  or 
one  intermediate  to  another.  Many  dyestuffs  can  not  be  made  commercially  in  lota 
much  greater  than  100  pounds;  others  can  be  made  in  lots  of  1  ton,  but  the  manufar- 
tunng  unit,  as  a  rule,  is  small. 

GERMAN   INDUSTRY,   CAPITAL,   DIVIDENDS,   ETC. 

In  analyzing  the  organization  of  the  German  dyestuff  industry  it 
will  be  found  that  not  only  a  vast  amount  of  brain  effort  has  bern 
expended  m  its  creation  but  that  also  the  cash  investment  has  been 
extremely  large. 

There  are  now  22  German  establishments  devoted  to  the  manufac- 
ture of  coal-tar  colors.     Of  these  21  are  owned  by  joint-stock  com- 
panies.    The  combined  capitalization  of  the  21  companies   in  1913 
was  $36,700,000.     In  that  year  they  paid  dividends  amounting  to 
$11,600,000,  or  21.74  per  cent  of  the  nominal  capitalization. 

The  explanation  of  this  high  percentage  hes  in  the  fact  that  for 
many  years  the  industry  has  regularly  devoted  a  large  share  of  its 
profits  to  wntmg  off  the  real  estate  and  plant  accounts  and  to  new 
construction.  One  of  the  oldest  and  strongest  companies  has  a 
capital  of  $13,100,000.  Its  stock  seUs  at  600.  In  1913  its  net  profits 
were  $6,000,000,  nearly  one-half  of  the  capital.  One-third  of  this 
sum  was  devoted  to  a  sinking  fund  for  the  erection  of  new  plants  etc 
and  to  welfare  funds  for  operatives.     From  the  remainder  a  dividend 


DYESTUFFS  FOR  AMERICAN  INDUSTRIES. 


35 


of  28  per  cent  was  paid.  This  course  has  been  pursued  for  so  many 
years  that  it  is  now  estimated  that  at  least  $400,000,000  have  been 
invested  in  the  industry. 

It  is  worthy  of  note  that  the  next  most  remunerative  chemical 
industries  in  Uermany  are  those  devoted  to  explosives,  glass,  heavy 
chemicals,  metallurgy,  soap,  and  candles.  The  factories  number  252. 
Dividends  range  from  11.2  to  11.8  per  cent.  Most  of  the  remaining 
chemical  industries  in  the  Empire  pay  dividends  of  5  to  10  per  cent. 

It  is  easily  seen  that  financially  the  German  coal-tar  dye  mdustry 
is  exceptionally  well  fortified  and  in  a  position  to  resist  powerfully 
any  attempt  to  destroy  its  supremacy. 

GEOGRAPHY  OF  THE  GERMAN  INDUSTRY. 

A  marked  feature  of  the  industry  is  its  concentration.  The  plants 
are  all  located  within  an  area  forming  a  square,  with  sides  of  300 
miles.  The  actual  concentration  is  even  more  pronounced,  for, 
with  the  exception  of  the  big  works  at  Berlin,  all  the  leading  estab- 
lishments, as  well  as  the  coke  fields  supplying  the  tar  and  the  benzol, 
are  situated  on  the  Rhine  and  its  tnbutaries,  in  a  narrow  strip  of 
territory  less  than  200  miles  in  length.  This  means  cheap  haulage 
for  the  bulkier  raw  materials  and  facilities  for  the  economical  dis- 
tribution of  finished  products  by  water  to  all  parts  of  the  world. 

If  an  industrv  of  this  size  in  the  United  States,  doing  an  extensive 
trans-Atlantic  Dusiness,  were  located  chiefly  along  the  banks  of  the 
Hudson,  between  Albany  and  New  York,  and  obtained  most  of  its 
raw  material  and  fuel  supply  within  short  distances  from  the  river, 
the  concentration  would  oe  practically  the  same.  These  conditions 
are  readily  seen  in  the  accompanying  map. 

RELATIONS   BETWEEN    COMPANIES. 

The  advantages  of  this  close  concentration,  permitting  easy  com- 
munication and  transfer  of  products  between  different  factories,  are 
intensified  by  the  close  relations  between  the  several  companies. 
Three  of  the  largest  organizations  are  closely  alhed;  three  other 
powerful  companies  form  another  combine.  The  relations  between 
the  two  big  units  are,  however,  friendly,  and  this  is  the  case  also 
with  the  relations  between  the  larger  and  the  smaller  firms.  There 
is  keen  competition  to  maintain  high  standards  of  excellence  in 
products  ana  to  diminish  the  cost  of  production,  as  well  as  to  bring 
out  new  dyestuffs;  but  there  is  a  well-organized  combination  to 
maintain  prices  and  to  render  mutual  assistance  in  utihzing  inter- 
mediates and  by-products.  For  practical  purposes  the  industry  is  a 
unit,  especially  in  all  that  concerns  its  dealing  with  foreign  markets 
and  with  foreign  attempts  at  competition.  These  trade  agreements 
and  cooperative  arrangements  seem  to  have  prevented  the  appear- 
ance of  rivals  on  German  soil  during  recent  years.  They  have  made 
themselves  frequently  felt  on  this  side  of  the  ocean,  as  efforts  have 
been  exerted  from  time  to  time  to  secure  emancipation  from  de- 
pendence upon  German  intermediates  or  finished  products. 


i 


36 


DYESTUFFS  FOB  AMERICAN  INDUSTRIES. 


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DYESTUFFS  FOR  AMERICAN  INDUSTRIES. 
EQUIPMENT  OF  PLANTS. 


37 


As  the  general  industry  has  developed,  the  individual  companies 
have,  in  several  cases,  widely  extended  their  operations,  so  as  to 
manufacture  all  or  nearly  aU  of  the  intermediates  required  in  their 
processes  and  a  large  share  of  the  heavy  chemicals  needed.  They 
nave  gone  outside  the  hmits  of  color  chemistry  and  manufactured 
a  variety  of  synthetic  medicinal  preparations,  several  synthetic  per- 
fumes, and  some  important  photographic  chemicals,  as  well  as  mater- 
ials for  modem  high  explosives.  This  has  meant  a  great  diversity 
of  eq^uipment  and  a  delicate  adjustment  of  manufacture,  so  as  to 
permit  the  complete  utihzation  of  all  by-products.  In  this  respect 
the  coal-tar  chemical  industry  shows  a  marked  resemblance  to  the 
great  American  packing  industries.  Starting  with  10  crude  coal-tar 
compounds,  it  produces  a  host  of  valuable  articles,  but  finds  methods 
of  utilizing  and  deriving  profit  from  all  its  by-products.  If  any  such 
compoimds  occur  in  the  evolution  of  a  new  product,  and  threaten 
waste  and  loss,  they  are  transformed  into  otner  new  preparations, 
for  which  uses  can  be  created. 

All  of  this  involves  extended  application  of  chemical  engineering, 
and  means  the  employment  of  a  wide  range  of  technical  devices. 

A  couple  of  examples  may  be  cited  as  showing  the  extensive  plant, 
and  staff  and  output  of  German  works  and  the  rate  of  expansion. 

The  famous  ^Tarbwerke"  at  Hochst  started  in  1863  with  5  work- 
men, making  the  few  anihne  dyes  then  known.  By  1888  it  employed 
1,860  workmen  and  57  cheimsts,  and  utilized  1,840  horsepower  in 
its  steam  engines.  It  then  produced  1,750  different  colors.  In 
1912,  30,000  norsepower  were  required.  The  staff  included  7,680 
workmen,  374  foremen,  307  chemists,  and  74  engineers.  Wages 
amounted  to  $2,050,000,  and  salaries  and  bonuses  to  $1,240,000. 
The  number  of  colors  reached  11,000.  Synthetic  alizarin  and  indigo 
were  leading  products,  and  such  materials  as  antipyrine,  tuberculin, 
and  diphtheria  serum  were  made  on  a  laige  scale. 

A  stiU  larger  estabhshment  is  the  Badische  Anilin-  und  Soda 
Fabrik,  near  Mannheim  on  the  Rhine.  It  covers  about  500  acres, 
with  a  water  front  of  a  mile  and  a  half  on  the  Rhine.  The  buildings 
cover  100  acres.  Transportation  between  the  several  himdred  build- 
ings is  effected  by  42  miles  of  railway.  Power  is  generated  and 
transmitted  by  158  boilers,  386  steam  engines,  and  472  electric 
motors.  Steam  fire  engines  number  25,  and  there  are  400  telephones. 
Each  day  there  is  a  consumption  of  1,000  tons  of  coal,  40  tons  of  ice, 
40,000,000  gallons  of  water,  and  2,500,000  cubic  feet  of  gas.  In 
1908  workmen  numbered  8,000,  chemists  217,  engineers  142,  and 
the  commercial  staff  918. 

WAGES  IN  THE  GERMAN  FACTORIES. 

The  participation  of  labor  in  the  cost  of  finished  dyes  is  not  high. 
It  ranges  from  10  to  15  per  cent,  and  is  usually  nearer  the  lower 
figure.  There  has  been,  however,  a  steady  increase  in  the  average 
wage  rate  of  late  years.  The  average  dailv  wage  in  Germany  for 
all  labor — ^boys,  and  common  and  skflled  labor — was  $0.65  in  1886. 
In  1908  it  had  reached  $1.14,  an  increase  of  77  per  cent.  In  1906  the 
average  daily  wage  in  the  Badische  works  for  a  •  10-hour  day  was 
$1.04.     To  the  normal  wage  should  be  added  the  contribution  by 


p 


^ 


38 


DYESTUFFS  FOR  AMERICAN  INDUSTRIES. 


DYESTUFFS  FOR  AMERICAN  INDUSTRIES. 


39 


emplovers  to  the  State  old-age,  accident,  and  sick  funds,  bonuses 
gained  by  many  workmen,  and  the  gifts  for  general  welfare.  In  the 
case  of  the  Badische  this  gift  was  $750,000  in  1908.  Including 
these  various  items,  it  may  be  assumed  that  the  prevalent  adult 
daily  wage  in  the  dyestuff  works  is  now  about  $  1 .80,  as  far  as  the  actual 
outlay  by  the  employers  is  concerned. 

A  lai^e  item  in  the  cost  of  production  is  due  to  the  salaries  of 
well-trained,  competent  chemists  and  engineers,  who  supervise  every 
step  of  the  multitudinous  processes.  Thus,  the  '^Badische"  employs 
30  well-equipped  chemists — university  graduates — in  the  research 
laboratory  alone,  quite  apart  from  the  manufacturing  staff. 

PROCESSES  OF  MANUFACTURE. 

The  chief  processes  employed  in  transforming  the  10  coal-tar 
"crudes"  into  nearly  300  intermediates  required  for  the  direct  pro- 
duction of  dyestuff s  are  11  in  number.  Shghtly  varied  in  individual 
cases,  they  constitute  the  great  bulk  of  the  operations  performed  in 
color  works.  They  are  of  such  fundamental  importance  that  a 
brief  description  is  desirable  in  order  to  bring  out  clearly  the  high 
degree  of  correlation  and  coordination  that  characterizes  the  in- 
dustry. These  processes  are  (1)  nitration,  (2)  chlorination,  (3)  sul- 
phonation,  (4)  reduction,  (5)  oxidation,  (6)  caustic  fusion,  (7)  alkyla- 
tion  (8)  liming,  (9)  condensation,  (10)  carboxylation,  (11)  diazo- 
tizing  and  coupung. 

(1)  Nitration. — An  aromatic  compound  is  treated  with  a  mixture 
of  nitric  acid  and  sulphuric  acid.  As  a  result  usually  one,  but  some- 
times two  or  three,  atoms  of  hydrogen  are  replaced  by  the  nitro 
group,  NOj.  The  extent  and  nature  of  the  reaction  are  largely 
effected  by  the  factors  of  time,  temperature,  and  proportions.  Usu- 
ally the  residual,  somewhat  dilutea,  sulphuric  acid  can  be  concen- 
trated and  used  repeatedly. 

(2)  Chlorination. — ^Action  of  dry  chlorine  gas.  The  gas  is  usually 
obtained  in  connection  with  the  electrolytic  production  of  caustic 
soda  from  salt,  is  liquified  for  transportation,  and  allowed  to  vola- 
tilize as  needed.  The  reaction  is  not  so  easily  controlled  as  nitration 
and  a  variety  of  substitution  products  are  often  the  result,  causing 
much  difficulty  in  separation.  One-half  of  the  chlorine  employed  is 
recovered  in  the  form  of  hydrochloric  acid.  The  synthetic  produc- 
tion of  indigo  involves  the  use  annually  of  over  5,000  tons  of  cnlorine, 
prepared  simultaneously  with  nearly  6,000  tons  of  caustic  soda,  and 
yielding,  as  by-product,  nearly  8,000  tons  of  33  per  cent  hydro- 
chloric acid. 

(3)  SulpTionation. — The  action  of  fuming  sulphuric  acid,  usually  in 
very  large  excess,  to  act  as  a  vehicle.  The  reaction  is,  in  a  few  cases, 
easily  controlled.  In  most  instances  a  variety  of  sulpho-acids  are 
obtained,  requiring  separation,  and  involving  the  problem  of  utiUza- 
tion.     The  excess  of  sulphuric  acid  is  generally  lost. 

(4)  Reduction. — The  substitution  of  hydrogen  for  oxygen  in  nitro- 
compounds, forming  the  corresponding  amido-bodies.  Thus,  benzol 
is  changed  by  nitration  to  nitrobenzol  and  that,  by  reduction,  to 
amidobenzol,  or  aniline.  Iron  fiUngs  or  turning,  with  acetic  or 
sulphuric  acid,  form  the  usual  reducmg  agents.  The  resultant  iron 
salts  are  without  value. 


\l 


;  f 


h 


(5)  Oxidation. — Potassium  bichromate,  potassium  chlorate,  lead 
peroxide,  manganese  dioxide  or  a  permanganate,  with  hydrochloric 
acid  or  sulphuric  acid,  are  the  usual  reagents.  The  residues,  chrome 
alum,  potassium  chloride,  etc.,  are  all  susceptible  of  utilization. 

(6)  Caustic  fusion. — ^The  operation  is  performed  chiefly  with 
sulpho-acids.  As  a  result  the  sulpho-group  is  replaced  by  hydroxyl. 
Thus  benzol  monosulpho-acid,  on  fusion  with  caustic  soda,  gives 
phenol,  or  carbohc  acid.  The  residue  of  sodium  sulphite  is  some- 
times used  in  making  bisulphite,  more  often  discarded.  The  oper- 
ation is  one  requiring  unusual  care,  and  the  results  are  often  variaole. 

(7)  Alkylation. — ^The  introduction  into  hydroxyl  or  amido  groups 
of  the  radicals  methyl  or  ethyl,  present  in  wood,  alcohol  ana  grain 
alcohol.  The  alcohols,  or  methyl  or  ethyl  chloride,  are  used,  along 
with  hydrochloric  acid,  and  the  operation  is  effected  at  elevated 
temperatures  under  pressure  in  autoclaves. 

(8)  Liming. — ^The  use  of  Hme  or  chalk  to  effect  separations  in 
mixtures,  especially  of  sulpho-acids,  through  the  differing  solubil- 
ities of  the  calcium  salts.  Sometimes  the  purpose  is  to  decompose 
chlorides  and  effect  the  separation  of  resultant  acids  and  aldehydes. 

(9)  Condensation. — ^A  large  class  of  operations  in  which  two  mole- 
cules of  the  same  substance,  or  of  different  substances,  unite  to 
form  a  new  compound,  with  the  eUmination  of  water,  or  ammonia, 
or  hydrochloric  acid.  Sulphuric  acid  in  considerable  excess  is  the 
usual  condensing  agent.  When  used  it  reappears  as  a  spent  acid, 
too  weak  to  admit  of  profitable  recovery.  Otner  condensers  are  the 
chlorides  of  zinc,  aluminum,  antimony,  sulphur,  and  phosphorus. 
In  most  cases  they  can  be  recovered  at  slight  cost  and  used  repeatedly. 

(10)  Carboxylation. — The  introduction  of  the  acid  carboxyl  group, 
by  the  joint  action  of  caustic  soda  and  carbon  dioxide  on  phenol  and 
its  homologues.  Thus  phenol  gives  saUcyUc  acid;  a-naphthol  gives 
oxy-naphthoic  acid.  The  alkaU  is  recovered  in  the  form  of  chloride 
or  sulpnate. 

(11)  Diazotizing  and  coupling. — ^An  aromatic  amine  reacts  with 
nitrous  acid,  forming  a  diazo-compound.  Thus  aniUne  yields  diazo- 
benzol.  Such  a  diazo-compound  m  the  presence  usually  of  sodium 
acetate  unites  readily  with  a  variety  oi  aromatic  substances;  the 
operation  is  termed  coupling.  The  product  of  such  a  reaction  spHts 
up,  yielding  the  original  amine  and  the  amido-derivative  of  the 
second  substance  employed.  Thus,  salicyUc  acid,  by  coupling  with 
a  diazo-compound  and  subsequent  reduction,  is  changed  into  amido- 
salicylic  acia,  an  intermediate  of  widespread  use.  'fiiis  sequence  of 
reactions  is  of  prime  importance.  It  serves  to  produce  a  variety  of 
intermediates,  and  is  the  fundamental  operation  in  the  manufacture 
of  the  so-called  azo  dyes,  which  constitute  about  one-half  of  the 
number  of  artificial  dyes  now  current  in  the  world's  trade. 

The  purely  chemical  transformations  fail  to  reveal  the  full  extent 
of  the  seauence  of  operations  in  eventually  obtaining  intermediates 
from  cruaes  by  a  chain  of  reactions.  Between  any  two  successive 
chemical  changes  there  are  from  one  to  three  mechanical  operations, 
such  as  baking,  boiling  filtering,  precipitating,  blowing  off  with 
steam,  and  the  like.  There  are  also  minor  chemical  operations, 
such  as  the  change  of  acids  or  bases  into  salts ;  the  separation  of  salts 
from  liquids;  their  purification,  drying,  and  storing,  etc. 


40 


DYESTUPFS  FOR  AMERICAN  INDUSTRIES. 


In  the  preparation  of  about  300  intermediates  by  the  use  of  these 
IL^r^  ?^  reactions  there  is  encountered  the  gi4te8t  d'versitHf 
problems  to  be  handled.  Every  step  involves  SenroHnpH^^^ 
compounds  other  than  the  one  ^ainly^  so^r  How  Cli^t  the^^ 
appearance  so  far  as  possible,  how  to  utUife  them  when  Stablv 
formed,  how  to  adjust  and  balance  the  consLSn  of  all  KrS 

S.^''  5'?^^'T  ^^f^  ^"^^"^  exceptional  technical  ai^d  busCi 
abihty  and  the  closest  cooperation  between  the  manufacture  and 
the  commercial  staffs  of  an  organization.  ^ 

UNIFORMITY  OF  PRODUCT. 

«f,^?  ^l  the  most  serious  demands  on  the  technical  staff  of  a  dve- 
stuff  factory  IS  the  necessity  of  obtaining  the  highest  uniformitv  h^ 
finished  products.     Standards  of  purity\re  nol  very  riSr  fc 
m^tJr  ^'l^y^l^^  ^o  sever^B  tesi.     This  mean^  S  ref^ 

STdvitur  fI"  fV'^'"^  ?^'^^  P^^^^  i^  ^^  ^^olutfon 

Tfa^  S  Exhaustive  and  careful  tests  are  essential  at  each 

?ioition  '%^'^'^'.'  T  ^5  .^^bmitted  to  a  new  chemfcd 
transformation.  The  margin  allowed  for  variation  from  the  standarrl 
of  purity  IS  very  slight.  In  some  instances  the  presence  La  c^^^^^ 
mtermediate  of  as  httle  as  one-fifth  of  1  per  cen^of  a  closely  E 

hSni^^sTulrut^^^^^  '''  P-^"^^^-'  woSttro- 

Tn^Lf  ^^  ""^^^  ^Z  *^'^  complexity  of  the  manufacturing  problem 
In  fact,  at  every  stage  the  artificial-dyestuff  industry  presents  a 
marvelous  maze  of  materials  and  operations,  interdependent  and 
closely  interlocked  technicaUy  and  economicaUy.         ""^P^^^^^^  ^^^^ 

TYPICAL  PHASES. 

Tlie  astounding  complexity  of  the  manufacture  as  a  whole  has  re 

C.  Hesse,  m  comprehensive  presentations  of  the  entire  series  of  onera 
tions  mvplved  m  the  production  of  certain  classes  of  dyes      K 
his  permission  summaries  of  some  of  the  more  strikin/phas^  of 
manufacture,  as  admn-ably  outhned  by  him,  are  presented.^ 
,    1  he  current  types  of  dyes  now  number  921.     Each  one   as  a  rule 
IS  oflFered  commercially  fn  a  variety  of  brands,  differing  minuTelv 

ceTai^'textnt"  Th^r'  '\t'^  "'  ^  'I'  avaUabihty  ?o^r  useS 
certam  textiles.     There  are  thus  many  thousand  distinct  brands  for 

These  921  dyes  are  divided  into  17  separate  chemical  classes    as 
shown  in  the  table  that  follows:  c"ii^«u  classes,  as 


Classes  of  dyes. 


Alizarin  and  anthraquinone 

Indigo 

Aw) 

Tri-  and  di-phenylmethane 

Sulphide 

Oxazin  and  thiazin . . ,', 
Xanthone 


Pyrazolone 

Stilbene 

Acridin 

Nitro,  nitroso,  aurflinlneVchinoUn*  thio^ 
benzyl,  and  indophenol 

Total 


20 


921 


DYESTUFFS  FOR  AMERICAN  INDUSTRIES.  41 

ILLUSTRATIVE  OUTLINES. 
ALIZARIN,  NAPHTHOL  YELLOW,  MAGENTA. 

Some  of  the  simpler  tynes  of  production  may  first  be  presented. 
Crudes,  intermediates,  and  final  dyes  are  distinguished  by  capitals. 
Operations  are  in  parentheses. 

Sequence  of  operations  in  alizarin  manufacture: 

ANTHRACENE 
(oxidation) 


ANTHRAQUINONE 

(sulphonation) 


ANTHRAQUINONE  MONOSULPHO-ACID 
(fusion  with  caustic  soda  and  chlorate) 


ALIZARIN 

There  are  here  only  three  chemical  transformations, 
guinone  serves  also  as  the  starting  point  for  a  variety 
dyes.  Alizarin  has  been  the  source  of  a  vast  amount 
Germany  since  its  discovery  in  1869,  when  it  began 
madder.  The  patent  rights  expired  in  1886,  but  its 
has  never  been  attempted  in  the  United  States. 

Operations  in  manufacture  of  naphthol  yellxm: 

NAPHTHALENE 

(sulphonation) 


The  anthra- 
of  important 
of  wealth  to 
to  supersede 
manufacture 


I 


A-MONOSULPHO-ACID 
(fusion  with  caustic  soda) 


^Hl 


A-NAPHTHOL 

(sulphonation) 


A-NAPHTHOL  TRISULPHO-ACID 

(nitration) 


NAPHTHOL  YELLOW. 


It 


This  IS  one  of  the  earher  standard  dyes.  Patent  rights  expired  in 
1897.  Some  has  been  manufactured  in  this  country  from  imported 
a-naphthol  trisulpho-acid,  the  last  transformation  being  compara- 
tively easy.    Practically  none  is  made  here. 


K 


42 


DYESTUFFS  FOR  AMERICAN  INDUSTRIES. 


Operations  in  manufacture  of  magenta: 


BENZOL 

(nitration) 


i, 


NITROBENZOL 
(reduction) 


1, 


ANILINE 
(reaction  with  o-  and  p-  toluidine,  and  o-  and  p-  nitrotoluol) 


,1 


MAGENTA  BASE 
(treatment  with  hydrochloric  acid) 


rT^ 


MAGENTA  DYE 

Preparation  of  nitrotoluol  and  toluidine: 

TOLUOL 
(nitration) 


[T] 


o-  and  p-  NITROTOLUOL 
(reduction) 

o-  and  p-  TOLUIDINE. 

Magenta  is  a  dyestuff  largely  used  in  the  United  States.  It  is 
made  here  to  some  extent,  but  the  manufactiu-e  is  confined  to  the 
final  step,  the  action  of  hydrochloric  acid  on  the  magenta  base.  In 
$1,000  worth  of  magenta  the  hydrochloric  acid  participates  to  the 
extent  of  about  $5.50. 

HTDROQUINONE   AND   SYNTHETIC   INDIGO. 

Following  are  the  operations  in  the  manufacture  of  hydroquinone: 

BENZOL 

(nitration) 


,1, 


NITROBENZOL 
(reduction) 


i, 


ANILINE 
(oxidation) 


m 


QUINONE 
(reduction) 


HYDROQUINONE 

Hydroquinone,  while  not  a  dye,  is  used  in  great  amounts  as  a 
photographic  developer,  and  is  an  important  accessory  product  of 
German  factories.  It  is  made  to  some  extent  in  the  limited  States 
from  imported  or  domestic  aniline. 


DYESTUFFS  FOR  AMERICAN  INDUSTRIES. 


43 


There  are  four  methods  of  making  indigo, 
and  the  fourth  from  naphthalene. 


Three  start  from  benzol 


BENZOL 
(nitration) 


NITROBENZOL 

(reduction) 


,1, 


ANILINE 
(treatment  with  chlor-acetic  acid) 


PHENYL  GLYCINE 
(fusion  with  sodium  oxide) 


i 


INDOXYL 
(air  blast) 


INDIGO 

The  crucial  point  in  the  sequence  is  the  transformation  of  phenyl 
ghrcine  into  indoxyl.  An  older  method  used  fusion  with  caustic  soda. 
The  yield  was  about  45  per  cent.  A  later  process  made  use  of  sodium 
amide,  with  nearly  quantitative  results.  A  still  later  process  substi- 
tuted advantageously  sodium  oxide  for  the  amide. 

The  manufacture  from  naphthalene  is  slightly  more  involved: 

NAPHTHALENE 

(oxidation) 


i, 


PHTHALIC  ANHYDRIDE 

(action  of  ammonia) 


PHTHALAMID 
(action  of  sodium  hypochlorite) 


ANTHRANILIC  ACID 
(action  of  chlor-acetic  acid) 


PHENYL  GLYCINE  A-CARBOXYLIC  ACID 
(fusion  with  caustic  soda) 


i 


INDOXYL 
(air  blast) 


INDIGO 

The  development  of  this  industry  illustrates  the  influence  of  quan- 
tities. This  last  method  was  the  first  to  be  used  successfully  on  a 
conmaercial  basis.  This  was  due  primarily  to  the  fact  that  at  that 
time,  by  fusion  with  caustic,  90  per  cent  of  the  phenyl  glycine  com- 
pound could  be  changed  into  indoxyl.  It  was  also  largely  due  to 
the  fact  that  naphthalene  could  be  had  in  abundance,  and  was  seek- 
ing a  market.     Pure  benzol  could  be  secured,  but  the  preparation  of 


il 


44 


DTESTUFFS  FOE  AMERICAN  INDUSTRIES. 


DYESTUFPS  FOE  AMEEICAN  INDUSTEIES. 


45 


of  rdrgorS?LtCraSl^^^^^  ''''  ^^'^i^''  consumption 

large  amouTof  tXoT  for  whilT"^**"''''"^  production  of  a  very 

industry,  and  how  in  dl  bran^he«  .   ''%*'-^  matenaJs  in  the  /yestuff 

be  maintWed  i^  ordefto  ^s2e  tt  h  r  '"^*"'^  ?^  P*'^^'-  >""«* 
interesting  to  note  that  tTp  fit.*     t  highest  economic  results.     It  is 

involves  tie  usnUplSaSgd?  dL^pr^LrAl^^^^  ^^^ 
sumption  of  80,000  tons  of  50  oer  CMit  nw^If  tk  ^  ui^  """"^  *^°°- 
empfoyed  represents  an  annuaTconTuSo^'of  IsoS  to^Tf*' 1  * -'1 
acetic  acid,  and  5,000  tons  of  liquid  cmS!  ^  **"** 

THE    KETONE   DYES. 

ca£  tSVer^l^rd^nrrsl^^^^^^  "'"'''  ^^^.7  "^  - 
closely  related  cheSuv    fn.l?.5?  ^  ^®  summarized.     Tfiese  are 

the  17  classes   andXw  howfw  representatives  from  several  of 
locked  with  oAe  anothe^    The  2?Hvif?^,K-''^  interlaced  and  inter- 
fortieth  of  the  total  nLbet  of  cJ^l\%*ves^T.f/"'^"'"^^^ 
seUers.     Most  have  been  in  use  30  ve^i^      F^t;       ^^  *'"  ^  g«°<l 
m  our  country.    American  mff  »rif  ^t  ^'gnt  were  never  patented 

expire  on  fouJin  ^:rrs"eK";L'r  rndTn^fifTh  1^25^"'  ^" 

tei'eV^a"errkrn:^'''ff|  in>.akm.  LS'oKS'  dves  is 

bonyl  chloride  on  dimethyl  anuLe     T^Tw^- ^'^^  r?''°"  «^<'«^- 

anihne  salt,  and  wood  Xhol      AniW  ^    *i  "  ?**^*  ^''"°  »°""»«- 

from  benzo   by  nitration  and  redm^W^f^i./  ""**'''  '^  '""''« 

Carbonyl  cHoride  Sts  W  tK         "^^he  resultant  nitrobenzol. 

oxide  an/cZ^d^e  in Te  pr^Zce  „'f  T^^T  ^*^^""  *'»^l>«'»  ™°n- 
num  or  animal  ch^cod.^  fn  a  cun-enT''nr^o^'''V  '"""^  f  P^««- 
calcmm  chloride,  lime  and  coke  »Zh^!i  5  "  *^  ""{  manufacture, 
The  carbonyl  chioride  sTevoW  U        a      "\  *"  ^'^^t""  f"™ace 

The  gas  is  Jassed^to^h^uid  diLettvT^nr"''  *°*f  'i^^''^  «*  8°  C. 
increlsed  40  per  cent  thp  r»r^f-  ^  •  *"'^*'  ,""^'^  **>«  weight  has 
several  W^at  1W»  C  Ae  rS«n1  ?°fPJ'"?d  by  heatV  for 
at  174°  C.  ®  resultant  ketone  is  a  solid,  melting 

By  using  grain  alcohol  instead  of  wood  alcnbnl  th^ 
ethyl  compound  is  secured.     tJ Ts'^^^j'V^i^^^^^^ 

2L2"  poLr^^^^^  and  dimethyl  aniline 

pouncis  of  ketone  landed!  ^       ^^  ""^"^^^  ^^^  ^^^^y   100 

In  making  dyes  by  the  aid  of  ketone,  "  condensation  "  f « t.      i 
Ine  ketone  and  another  poaI  fo,.  ^«J      V"""^"saiion     takes  place. 

in  the  presence  of  phospWrtri^^^^^  T^"^  ^P^^  ^^^^  "^^her 

The  co^x  dye  S,  3  h^^^^^^ 

are  by-products.     The  latter  c/nh^nhlr.     a        •     .Phosphonc  acid 
oxycliloride  for  renewed  use.  ^^"^  ^^^"^  "'^^  phosphorus 


«M 


In  making  100  pounds  of  ketone  and  in  using  it  to  produce  dyes, 
a  total  amount  of  100  pounds  of  33  per  cent  hydrocnloric  acid  is 
released.  Of  this  about  30  pounds  are  utilized  to  prepare  salts  of 
basic  dyes  produced.     The  remainder  is  available  for  other  purposes. 

In  making  and  using  the  ketone,  four  of  the  eleven  general  opera- 
tions required  in  dye  manufacture  come  into  play,  viz,  nitration, 
reduction,  alkylation,  and  condensation.  The  materials  employed 
are  benzol,  coke,  phosphorus,  chlorine,  nitric  acid,  sulphuric  acid, 
hydrochloric  acid,  iron  fiUngs.  Intermediates  formed  are  nitro- 
benzol, anihne,  dimethyl  anilme,  carbonyl  chloride. 

Turning  now  to  the  production  of  the  24  dyes  in  question,  it  is 
found  that  23  final  intermediates  are  necessary.  The  total  number 
of  operations  requisite  to  produce  these  final  intermediates,  starting 
in  each  case  from  coal-tar  crudes,  is  118.  Derivatives  of  benzol, 
toluol,  naphthalene,  and  phenol  appear  in  the  combinations  effected. 
In  16  cases  a  single  coal-tar  crude  is  represented;  in  the  remaining 
cases,  two  are  present.     On  an  average  5  transformations  are  re- 

Suired  to  produce  a  final  intermediate  ready  to  condense  with  ketone. 
I,eduction  occurs  31  times,  nitration  21  times,  sulphonation  13  times, 
oxidation  12  times,  condensation  11  times,  etc. 

If  equal  amounts  of  ketone  were  used  to  manufacture  the  24  dyes, 
using  in  each  case  100  pounds,  the  total  2,400  pounds  of  ketone  would 
produce  4,605  pounds  of  finished  dyes.  In  this  final  product  different 
constituents  would  participate  as  follows:  Ketone,  52.11  per  cent; 
benzol,  7.58  per  cent;  toluol,  5.21  per  cent;  naphthalene,  11.42  per 
cent;  phenol,  1.69  per  cent;  from  sulphonation,  alkylation,  etc.,  21.99 
per  cent.  Benzol,  however,  constitutes  58.21  per  cent  of  the  ketone 
used,  so  that  the  total  participation  of  this  hydrocarbon  in  the  dyes 
would  average  37.91  per  cent. 

Naturally  these  24  dyes  are  not  required  by  the  trade  in  approxi- 
mately equal  amounts.  In  constructing  a  plant  for  their  manufac- 
ture a  high  degree  of  intelligence  is  imperative,  in  order  to  avoid 
waste  of  time,  space,  and  apparatus,  in  planning  the  size  and  relative 
position  of  the  different  buildings. 

To  effect  the  118  operations  it  is  not  necessary  to  have  that  number 
of  sets  of  apparatus.  The  11  major  operations  require,  however, 
in  each  case,  equipment  varying  in  size,  etc.,  depending  upon  the 
materials  to  be  transformed,  their  relative  amounts,  the  time  for 
manufacture,  etc.  Thus  the  same  apparatus  for  nitration  is  not 
necessarily  adapted  for  use  with  both  benzol  and  naphthalene,  the 
same  condensation  apparatus  is  not  applicable  for  all  forms  of  con- 
I  densation,  etc. 

In  the  manufacture  of  this  group  of  24  dyes  there  are  several 
instances  where  operations  produce  two  or  more  products,  usually 
isomeric  compounds,  and  the  problem  of  complete  utihzation  is  pre- 
sented. 
I       When  chlorine  acts  upon  toluol,  three  substances,  in  varving  pro- 
j  portions,  are  always  formed — benzal  chloride,  benzyl  chloride,  benzo- 
»  trichloride.     Benzyl  chloride  serves  in  producing  3  dyes,  and  benzo- 
I  trichloride  1  dye,  in  the  group  of  24.     feenzal  chloride  is  not  utilized 
i  in  this  group,  but  it  serves  as  the  starting  point  for  the  manufacture 
^of  a  much  larger  group — the  benzaldehyde  dyes.     Again  in  nitrating 
toluol,  two  isomeric  products  are  always  formed — orthonitrotoluol 
and  paranitrotoluol.    The  latter  is  used  in  making  one  dye  of  the 


46 


DYESTUFFS  FOB  AMERICAN  INDUSTRIES. 


group  in  question.  The  ortho  variety  is,  however  of  much  wp^f ^r 
general  importance.  It  is  the  starting  'poinTfor  maUng  tSe 
fnl^n""  !?•  *'»'^t'tJ'«'»t  in  a  p,up  of  45  Syes.  The  ,Le  o?  the  Sra 
^Vt  wL'r  i^^  "A**'"''  "'Z  a  by-product  u^avoffly 
^voiZ^of  ra^SnSrss".'  °'  "'-"^-'-«'  -^^  the  consequent 
trJ^  *T"  "^^^^''f  illustrate  how  the  commercial  side  of  the  Indus- 

piuuucis  in  augnment,  with  avoidance  of  excess  nrodnrtinn  n™r 
market  requirements.  This  merchandizing  effort  mvolves  ^Tfi 
paii^taking  and  highly  developed  skill  involves  inlmite 

Ihe  group  of  24  dyes  includes  15  acid  and  9  basic  products      F.ir 

wJoiitrthTi^'o'f  th*e*T  "  ^"  '^'  ''^^  -oorJnd  5  morf'^n 
r^„r  **ie  aid  of  the  chrome  process.     One  is  emplovcd  in  calico 

T:^ci:T^r:il^&-^ '-  P^P-'  leatherfiu^te^'^ttiS 
FnZ?^  the  simplest  and  least  intricate  series  of  rortfoS  ia  tft 

BENZIDINE   DYES. 

nutbS  Rf  ^r  ''""'P^''-^  ^"MP  is  that  of  the  benzidine  dyes, 

srv'aS  'k^^ToTi^  LTotr '"''  ^  '^'"''^^'  "^  ^«-«i 

BENZOL 

(nitration) 


J, 


.  NITROBENZOL 

(fusion  with  caustic  soda  and  zinc  dust) 

HYDRAZOBENZOL 
(action  of  hydrochloric  acid) 


1, 


BENZIDINE 

;„  ^'^^  Mi'^Wer's  ketone  benzidine  itself  is  not  a  dyestuff     It  is  onlv 
in  combination  with  other  coal-tar  derivatives  that  it  rives  ris^  to 

H?i.  iffi  ?*"<    ^'^  r.^*""  ^  «ff««t  any  such  combinatio?The  b^nz* 
dme  IS  first  changed  by  the  action  o?  nitrous  acid  into  its  tetr^o 
derivative      In  this  form  it  reacts  with  some  44  intennedifttP«^« 

S^'^Tp.^^'r;*"'^  •*^^-,   ^"^  44  final  inten^ediates^re  feed ' 
from  benzol,  toluol,  xvlol,  phenol,  cresol,  and  naphthalene     E ' 

preparation  caUs  for  tfie  production  of  55  other  i^termeTatesnoT 
r.l^^in'H'T*  'taction  with  tetrazobenzidine.    The XivSnTs  '1 
Benzol  10   toluol  2,  xylol  1,  phenol  1,  cresol  2,  naphthdenr28 

nvea  Irom  the  44  final  intermediates.    Of  the  multitude    hnf  «•> 
have  won  a  recognized  position  in  the  field  of  dyel^  ' 


DVESTUFFS  FOR  AMERICAN  INDUSTRIES. 


47 


o 

n 


86201"— 15- 


48 


DYESTUFFS  FOB  AMERICAN   INDUSTRIES. 


DYESTUFFS  FOR  AMERICAN  INDUSTRIES. 


49 


The  average  number  of  transformations  required  to  make  final 
intermediates  from  naphthalene  is  4.5,  from  the  other  crudes  3.  As 
the  operations  requisite  to  prepare  tetrazobenzidine  and  its  final 
reaction  with  one  to  four  intermediates  are  5  in  number,  the  total 
number  of  chemical  changes  involved  in  the  manufacture  of  benzi- 
dine dyes  ranges  from  a  minimum  of  6  to  a  maximum  of  23.  The 
interdependence  is  illustrated  by  the  two  accompanying  charts. 

Benzidine  dyes  are  of  prime  importance,  as  they  dye  cotton  di- 
rectly without  the  use  of  a  mordant.  The  range  of  colors  and  shades 
is,  however,  inadequate  to  meet  the  demands  of  cotton  dyers. 

TOLIDINE   AND  ALLIED  DYES. 

In  order  to  fill  in  the  lacking  tints,  recourse  is  had  to  tolidine, 
dianisidine,  and  five  other  less  important  derivatives  of  benzidine. 
Together  these  yield  the  167  direct  cotton  dyes,  of  the  so-called 
diphenyl  type,  now  in  current  use.  They  are  divided  as  follows: 
Benzidine  82,  tohdine  43,  dianisidine  28,  a-nitrobenzidine  1 ,  dichlorben- 
zidine  3,  benzidine-monosulpho-acid  2,  benzidine-disulpho-acid  4, 
ethoxy-benzidine  4. 

These  complementary  substances  are  used  exactly  as  benzidine 
itself,  reacting  in  the  same  way  with  the  44  final  intermediates 
alreadv  mentioned.  They  require,  however,  for  the  production  of 
several  current  dyes,  a  number  of  additional  finished  intermediates, 
more  or  less  comphcated  in  their  relationship.  They  react  also  di- 
rectly with  phenol  and  cresol. 

Tolidine  is  made  from  o-nitrotoluol  in  the  same  manner  as  benzidine 
is  prepared  from  nitrobenzol. 

Together,  the  dyes  of  the  ketone,  benzidine,  tohdine,  etc.,  types 
form  about  one-fifth  of  the  current  artificial  colors. 

PATENTS  IN  THE  GERMAN  INDUSTRY. 

Patents  have  been  multitudinous  in  connection  with  the  evolution 
of  the  German  coal-tar  dyestuff  industry.  From  1876  to  1912  they 
numbered  8,062,  or  224  annually  on  an  average.  Many  correspond- 
ing patents  were  taken  out  in  other  lands,  especially  in  France  and 
Great  Britain.     The  number  in  the  United  States  was  2,432. 

But  very  few  of  the  important  intermediates  have  been  patented. 
Not  a  few  dyes  tuffs  have  been  patented  by  non-German  inventors. 
Most  patents  cover  a  vast  range  of  possibifities,  and  protect  the 
manufacture  of  thousands  of  theoretical  dyestuffs,  of  which  an  infini- 
tesimal number  ever  win  a  place  in  the  world's  markets.  It  is 
claimed  with  authority  that  not  over  1  per  cent  of  the  German 
patents  in  this  industry  have  ever  proved  remunerative.  In  the  case 
of  the  921  dyes  in  current  use  at  the  beginning  of  1913,  762  German 
patents  were  involved.  Of  these,  485  were  originally  patented  in  the 
United  States.  One-half  of  the  American  patents  have  expired. 
Many  of  the  remaining  patents  expire  this  vear  or  in  the  immediate 
future.  Over  50  per  cent  of  the  current  clyestuffs  were  never  pat- 
ented in  the  United  States. 

The  general  situation  shows  clearly  that,  as  far  as  patent  protection 
is  concerned,  numerous  dyes  have  been  patented  by  non-German 


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DYESTUFFS  FOR  AMERICAN  INDUSTRIES. 


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DYESTUFFS  FOR  AMERICAN   INDUSTRIES. 


51 


inventors,  that  many  dyestufFs  have  never  been  patented,  that  the 
patents  on  many  others  have  expired,  a  considerable  number  each 
year,  since  1880.  In  spite  of  aQ  this  apparent  freedom,  and  the 
absence  of  all  patentprotection  on  theproduction  of  the  intermediates 
requisite  for  dyestutt  manufacture,  efforts  m  other  coimtries  to  chal- 
lenge and  contest  Germany's  dominant  position  in  the  dyestuff  indus- 
try have  been  few,  and  practically  futile. 

As  a  matter  of  fact,  Germany  has  demonstrated  her  ability  to 
outrank  the  entire  world  in  making  patentable  compounds  from 
nonpatented  intermediates  and,  in  addition,  to  manufacture  these 
intermediates  in  open  competition  with  all  rivals. 

In  its  ultimate  analysis,  the  situation  shows  that  German  chemists 
and  captains  of  industry  have  actually  done  the  bulk  of  the  hard  and 
complicated  labor  inherent  in  the  creation  and  organization  of  a 
vast  branch  of  manufacture,  and  that  they  have  not  hesitated  to 
use  the  power  associated  with  its  hardly  won  national  predominance 
to  prevent  effectively  any  serious  competition  in  industrial  lands. 

AMERICAN  ATTITUDE  TOWARD  THE  GERMAN  INDUSTRY. 

The  inquiry  why  the  natural  resources  of  our  country  have  never 
been  utilized  on  any  extensive  scale  to  meet  the  needs  of  American 
consumers  and  create  a  distinctly  American  coal-tar  chemical  industry 
has  often  been  raised. 

The  few  American  manufacturers  of  artificial  dyestuffs  claimed  that 
they  were  doing  all  that  was  possible  under  existing  economic  and 
fiscal  conditions.  Consumers  of  dyestuffs  were,  as  a  rule,  indifferent, 
satisfied  to  receive  regularly  a  supply  of  all  needed  colors,  ordinarily 
uniform  in  strength  and  meeting  every  possible  requirement  in  shade 
or  adantability  to  fabric  and  material.  American  economists  dwelt 
upon  the  enormous  complexity  of  the  problem,  bristling  with  diffi- 
culties at  every  step,  should  any  attempt  be  made  to  dispute  the 
supremacy  of  the  foreign  industry,  intricate  and  complicated  beyond 
any  other  organized  field  of  human  effort  and  formidably  intrenched 
within  the  limits  of  a  single  powerful  nation. 

No  direct,  concrete  attempt  was  ever  made  to  focus  national 
thought  in  the  United  States  upon  the  problem,  to  enhst  the  coopera- 
tion and  combined  effort  of  producers  of  crude  products,  actual  or 
potential  manufacturers  of  fimshed  dyes,  the  many  trades  consuming 
dyestuffs  in  Quantity,  the  still  more  numerous  branches  dependent  in 
turn  upon  tnem,  and  the  general  industrial  world  in  seeking  an 
effective  solution  worthy  of  the  nation's  rank. 

The  present  crisis  in  the  world's  affairs,  threatening  to  interrupt 
any  day  the  customary  supply  of  artificial  dyestuffs,  lias  served  to 
awaken  general  attention  to  the  importance  ojt  this  national  question 
to  a  degree  never  attained  by  the  more  or  less  academic  discussions 
of  the  past.  A  famine  in  dyestuffs  strikes  at  the  very  existence  and 
profitable  continuance  of  a  large  group  of  industries.  American 
chemists  have  been  put  in  the  position  of  defending  themselves,  and 
explainmg  why  they  could  not,  at  once,  meet  the  Nation's  need  in  an 
emergency. 


52 


DYESTUPFS  FOR  AMERICAN  INDUSTRIES. 
PRODUCERS  OF  COAL-TAR  CRUDES. 


Those  in  control  of  our  coking  interests,  and  controlling  the  coal-tar 
branch,  are  thoroughly  sympathetic  to  any  prospective  enlargement 
of  the  demand  for  coal-tar  crudes.  Recovery  plants  for  benzol  and 
tar  m  coke  works  wiU  be  rapidly  increased,  tar  distilleries  will  erect 
the  requisite  plant  for  an  ample  supplj  of  the  requisite  10  coal-tar 
crudes,  just  as  soon  as  there  is  the  fairly  permanent  assurance  of  a 
regular  demand  for  the  products. 

MANUFACTURERS  OF  HEAVY  CHEMICALS. 

These  likewise  are  thoroughly  in  sympathy  with  the  creation  of  a 
krge  industry,  capable  of  using  great  amounts  of  staple  chemicals. 
There  does  not  seem  to  be  any  inclination  on  the  part  of  such  man- 
ufacturers to  embark  themselves  in  the  production  of  dyestuffs. 
There  is,  however,  a  distinct  readiness  to  cooperate,  by  organizing, 
on  a  modest  scale,  the  manufacture  of  the  leading  intermediated. 
One  firm  has  ventured  to  erect  a  somewhat  extensive  plant,  after 
successfully  estabhshing  the  manufacture  of  a  few  intermediates  of 
recognized  purity.  The  feeling  here  is,  however,  conservative. 
There  is  a  marked  disinclination  to  invest  considerable  amoimts, 
while  the  danger  is  present  of  awakenmg  sooner  or  later  the  determi- 
nation on  the  part  of  the  German  industry  to  throttle  any  too  am- 
bitious attempts  by  eflPective  and  persistent  selling  at  prices  under 
cost.  With  the  assurance  of  adequate  legislative  protection  against 
the  danger  of  ''dumping"  on  the  part  of  foreign  producers  of  coal-tar 
intermediates,  there  is  every  indication  that  existing  chemical  indus- 
tries would  embark  readily  and  extensively  in  the  production  of  this 
class  of  compounds. 

Hydroquinone,  the  well-known  photographic  developer,  falling 
practically  in  this  category  of  coal-tar  compounds,  although  not  used 
m  the  production  of  colors,  is  now  successfully  manufactured  by  an 
American  chemical  firm. 

MANUFACTURERS  OF  ARTIFICIAL  DYESTUFFS. 

In  this  class  there  is  no  question  of  a  readiness  to  advance  far 
beyond  the  modest  hmits  of  the  present  manufacture  as  soon  as 
adequate  legislation  is  assured.  The  manufacturers  assert  that  90 
per  cent,  by  value,  of  the  artificial  colors  used  in  the  United  States  are 
now  unprotected  by  patents,  or  will  be  freed  from  patent  protection 
within  two  or  three  years;  and,  further,  that  practically  all  of  the 
genuine  needs  of  American  colorists  are  covered  by  this  90  per  cent 
of  dyes. 

With  the  protection  of  an  effective  antidumping  clause,  they  feel 
that  much  can  be  done  toward  buUding  up  the  dyestuff  industry  in 
our  country.  The  manufacture  of  the  simpler  mtermediates,  and 
of  finished  dyes  involving  a  minimum  of  chemical  transformations, 
could  be  attempted  with  a  degree  of  security  and  confidence  now 
unknown. 

The  certainty  that  ruthless  and  prolonged  undersoUing  on  the  part 
of  foreign  competition  could  be  effectually  forestalled  would 
undoubtedly  stimulate  effort  in  several  directions  and  aid  in  gradually 
building  up  important  features  of  the  industry,  even  if  there  could  bo 


i 


DYESTUFFS  FOR  AMERICAN  INDUSTRIES. 


68 


'%- 


If  h 


no  attempt  at  creating  a  self-contained,  national,  dyestuff  industry 
in  the  immediate  future.  Instances  are  cited  where  such  an  exten- 
sion of  the  range  of  manufacture  of  intermediates  and  of  finished 
dyes  would  unquestionably  take  place.  Among  these  are  such 
important  intermediates  as  nitrobenzol,  aniline  oil,  and  salts,  resorcin, 
nitrophenol,  saUcyhc  acid,  benzaldehyde,  phthalic  acid,  the  naphthols 
and  the  naphthylamines.  Among  the  finished  dyes  are  a  variety  of 
colors  obtained  by  not  more  than  two  transformations  from  the 
above  list. 

There  is  some  feeling,  in  this  connection,  among  our  dyestuff  manu- 
facturers that  the  patent  laws  could  advantageously  be  modified,  so 
as  to  assure  the  working  on  American  soil  of  all  patents  granted  by 
our  Government.  Great  Britain  has  lately  made  changes  in  this 
direction  in  her  patent  laws.  Germany  has  for  years  required  that 
the  owiiers  of  a  patent  must  work  the  invention  to  an  adequate 
extent  in  the  Empire  or  do  all  that  is  necessary  to  secure  such  working. 
Otherwise,  if  deemed  needful  in  the  public  interest,  permissionTs 
granted  others  to  use  the  invention.  The  owner  of  the  patent  receives 
adequate  compensation,  and  the  manufacture  in  Germany  is  assured. 
It  is  claimed  that  if  such  legislation  had  been  in  force  30  to  40  years 
1^0,  when  invention  in  the  dyestuff  industry  was  at  its  height 
European  patentees  would  have  been  forced  to  build  branch  factories 
m  the  United  States.  These  factories  would  undoubtedly  have 
developed  other  products.  While  not  helping  the  then  existing 
American  factones,  a  large  dyestuff  industry  would  inevitably  ha^ 
been  created  on  American  soil,  with  resultant  benefit  to  the  country 
at  large.  "^ 

.    "^.^/^^^^^^  opinion   among  American   chemists   and   inventors 
in  this  field  is  antagonistic  to  such  legislation.     Its  evils,  it  is  claimed 
more  than  counterbalance  the  advantages.     Certainly  in  England 
it  has  not  aided  in  the  development  of  the  artificial-dyestuff  industry. 

CONSUMERS  OF  ARTIFICIAL  DYESTUFFS. 

The  great  textile  branches  and  the  other  branches  consummg  large 
amounts  of  dyestuffs  have  been  indifferent  or  lukewarm  in  the  pit 
to  the  question  of  an  American  color  industry.  Now  that  their 
normal  manufacture  is  threatened  by  dislocation,  they  are  more  keenly 
ahve  to  the  vital  character  of  the  subject.  The  chairman  of  the 
dyestuffs  committee  of  the  National  Association  of  Finishers  of  Cotton 
Products,  A.  L.  Lustig,  lately  stated  in  this  connection:  ^'The  textile 
tmisher  would  have  to  sacrifice  temporarily  in  some  directions  m  order 
to  accomplish  the  greatest  good  for  all,  which  would  be  a  gradual 
development  of  the  coal-tar  chemical  industry  in  the  United  States, 
ii-  •  "^^^  i^  would  be  good  business  judgment  on  our  part  to  bear 
additional  financial  burdens  for  some  years  to  come  in  order  to  help 
to  establish  an  American  coal-tar  chemical  industry  and  in  this  way 
ultimately  benefit  ourselves." 

Mr.  Lustig  is  strongly  of  the  opinion  that  by  cooperation  between 
the  American  manufacturmg  interests  and  the  German  color  makers 
much  could  be  accomplished,  that  we  could  gain  years  of  time,  save 
large  sums  of  money,  and  establish  the  industry  under  the  most 
favorable  conditions.  He  adds:  ^^The  German  people  will  require  aU 
theu-  hnancial  resources  to  repair  the  damages  caused  by  the  present 


54 


DYESTUFFS  FOB  AMERICAN  INDUSTRIES. 


rr,'  ''"^*t«y  cm  fumkh  m  with  patent  licenses  and  with  some  ex- 
work' o^t'thir^nl^h/"™  ?  nucleus%r  the  elaborate  step^  need^  to 

ZuhtZvtj^^^^""-  }  ^^'^^^  *^**  ^y  the  resulting  cooperation 
with  the  European  manufacturers  who,  at  the  proper  moment  m^hf 

W  ^?i^  ^i^'l^''  ^^*^'  "^  """"^^^'^P  toVablirSdX 
„t^tt.  •  ^J^'^^  manner  prevent  a  recurrence  of  the  conditions 
which  jeopardize  textile  interests  at  the  present  time;  this  Si  be 

S.Tta^''*'^"  "^  '""**"'^  '^'^'^  ^  ^^  Patent  laws  ch^^i  of 

,,nnn"^Lr?^""^^'^  ''^  ^I^-  "\  SU^ntities,  and  absolutely  dependent 
upon  certam  colors  unobtamable  at  present,  have  erected  emergency 
plants  and  produce  the  needed  dy^  at  some  considerable  bfS 
m  cost.     In  one  such  case  the  experiment  has  worked  so  well  tC 

SteSv  inT^iTP^^  ^T  ^?P^^^  •'^  readmess  to  embark 
extensively  m  the  industry  and  enlarge  steadily  its  present  modest 

^^'J r^A-^.-^^ r'^f  legislation  generally^demaS  ' 

t^  iA  .f  *  fu"'*'*  ^^^  ?"  th«  P""t  of  some  users  of  dyes  in  regard 
to  identifymg  themselves  with  any  concerted  move  to  favofthl  S 
lishment  of  an  American  dyestuff  industry.     Thev  state  frimll^fhaJ 

hZutrf  H  K '"?,  """'^  P^^'''/  result^  in  th4- tig  ilpdy 
blacklisted  by  all  unporters  of  cofore  and  cut  off  from  any  Tupplv  df 
dyes,  outside  of  the  Lmited  American  product.  ^'^^ 

ECONOMISTS. 

t;J?r^'^  f  growing  feeling  among  American  econombts  that  the 

time  13  npe  for  reaching  a  decision  whether  the  Unitod  States  is  ever 

to  have  a  coal-tar  chemical  industiy,  self-contained  and  independent 

utihzing  the  great  natural  resourc^'and  meeting  the  NaSneed^ 

as  fuUy  as  is  the  case  with  our  iron  and  steel  in^dustrv^or  a  score  of 

other  promment  phases  of  national  activity.    It  is  pointed  out  with 

force  t-hat  every  year  which  elapses  strengtiiens  relaCely  and  absS 

lutely  Germany's  predominance  in  this  ffeld  and  multioUrin^fr 

metrical  ratio  the  difficulties   to  be  overcome  sh^d   the  attorn^ 

ever  be  made  to  create  the  fully  equipped  American  bdust^     K 

seems  to  be  no  doubt  in  the  minds*^of  some  American  eTonomiste 

that  the  task  can  be  accompUshed,  and  that  the  present  worWrco^ 

juncture  offers  the  most  favorable  opportunity  for  takinrthe  initial 

and  fundamental  steps.     The  enactment  of  igislS  to  preven 

"dumpmg"  would  unouestionably  give  an   enormous  imDetuI^n 

American  enterprise  an3  capital,  aJreldy  attracted^  thisreFdBu? 

some  years  must  mevitably  elapse  before  a  scient  fie  and  technica 

staff  could  be  thoroughly  traine/and  before  such  captains  of  iStit 

could  be  evolved,  as  m  our  iron,  steel,  petroleum  electrical  a^d  of  hZ 

^orid'lelder'  P""  ""'  *'''''  foreigA^rivals,  and  often  rl^l^edt 

AMERICAN  CHEMICAL  SOCIETY.  NEW  YORK  SECTION. 

To  meet  a  widespread  demand  for  explanation    a  commitf p«  w«« 
appointed  by  the  l5[ew  York  section  of  ?he  AmericanTh^S 
ciety  to  report  upon  the  situation.     This  committee  was  composed  S 
the  foUowing  members:  J.  B.  Herreshoff,  representing  the^ranu 

ofcoair fc  f  r"^  V'-  .^l.^^""^'  -presenting  SfanufUfre^s 
01  coal-tar  colors,  J.  Memtt  Matthews,  representmg  the  textile  in ter- 


DYESTUFFS   FOR  AMERICAN  INDUSTRIES. 


55 


i 


* 

"*"««. 


*»•*. 


) 


» 


f 


/( 


ests;  H.  A.  Metz,  representing  the  importers;  David  W.  Jayne,  rep- 
resenting the  producers  of  crude  coal-tar  products;  Allen  Rogers, 
chauman  of  the  New  York  section;  and  Bemhard  C.  Hesse,  chemicai 
expert,  chairman. 

The  findings  of  this  committee  were  considered  on  November  9, 
1914,  in  detail,  and  after  discussion  the  report  was  unanimously 
adopted  by  the  section. 

Tne  committee's  conclusions  were  in  harmony  with  the  general 
expression  of  opinion  on  the  part  of  those  more  closely  concerned 
with  the  miestion,  consumers,  manufacturers,  and  others,  as  just 
outlined.  Special  stress  was  laid  in  the  report  upon  the  imperative 
necessitv  of  adequate  legislation  to  prevent  "dumping,"  or  under- 
selHng,  by  the  present  dominant  foreign  industrv  before  any  serious 
attempt  could  be  made  to  materially  enlarge  the  existing  scope  of 
American  dyestuff  manufacture. 

ESTABLISHMENT  OF  AN  AMERICAN  INDUSTRY. 

The  successive  steps  necessary  for  the  estabhshment  of  a  self-con- 
tained American  coal-tar  chemical  industry,  under  favoring  condi- 
tions, have  been  outhned  as  follows: 

1.  Determination  of  the  American  demand  for  dyestuff 8. — Statistics 
show  the  total  value  of  our  imports  of  foreign  dyes,  but  they  do  not 
show  the  exact  amounts  of  each  dye  consumed  m  the  United  States 
except  approximately  for  alizarin  and  indigo.  It  is  necessary  to 
take  a  census  in  order  to  have  the  data  for  planning  intelHgently  the 
different  phases  of  a  combined  manufacture  destined  to  supply  the 
entire  domestic  demand,  and  for  so  coordinating  the  various  features, 
as  to  secure  the  highest  economy.  This  is  not  an  easy  matter,  but 
it  IS  mdispensable.  The  information  might  be  secured  by  a  general 
communication  on  the  part  of  American  consumers  of  the  average 
annual  amounts  required  of  each  dyestuff.  It  might  be  obtained 
through  a  careful  collocation  of  the  data  contained  in  consular  invoices. 
Certainly  it  will  never  be  communicated  by  importers. 

2.  Research  laboratory.— AM  interested  parties  should  unite,  pos- 
sibly with  Federal  cooperation,  in  the  estabhshment  of  a  research 
laboratory  m  which  the  various  chemical,  mechanical,  and  engineering 
problems  connected  with  the  formation  of  each  intermediate  and  the 
production  of  each  finished  dye  could  all  be  solved  and  standardized. 
Further,  in  such  an  experimental  institute  the  entire  coordination  of 
the  industry,  on  the  basis  of  evenly  supplying  American  consumption 
could  be  carefully  determined.    .  ' 

3.  Evolution  of  the  productive  industry. — Simultaneously  with  the 
organization  of  such  a  laboratory,  existing  and  newly  formed  fac- 
tories could  start  units  of  production,  beginning  with  the  simpler 
dyes,  or  those  involving  a  minimum  of  transformations.  Graduallv 
the  volume  would  increase,  until  finally  the  entire  field  would  be 
covered.  The  central  research  laboratory  would  constantly  serve  as 
a  clearmg  house  to  plan  and  provide  agamst  waste  through  improper 
coordmation;  and  such  cordial  trade  cooperation  as  exists  between 
the  component  parts  of  the  German  industry  should  be  sought  for. 
At  the  same  time  our  schools  of  science  would  organize  special  courses 
to  train  up  the  necessary  corps  of  chemists  and  chemical  engineers  to 
naan  the  growing  industry,  exactly  as  they  have  done  for  the  exten- 
sive dyemg  and  bleaching  industries  of  our  country. 


56 


DYESTUFFS  FOE  AMEEICAN  INDUSTRIES. 


n, JA 1^^^  ^''}'t  ?.  '^^r'^^'  possibly  less,  before  the  industry  could 
Sni  iiH^r.t^"^H  ^''aT  °e«ds;  but  it  would  be  disSictly  a 
national  industry.  Here  and  there  a  minor  gap  must  be  fiUed  from 
abroad  until  patent  rights  have  expired.  Unquestionably  AmeriZ 
inventiye  gemus  woullbe  spurred  to  score  successes  in  the  n^  field 

THE  PROBLEM  IN  ENGLAND  AND  FRANCE. 

J=  ^Tt  Britam  is  a  countnr  m  which  the  artificial  dyestufiF  industry 
is  much  more  developed  t&an  in  the  United  States.     It  depS 

fmn,  X=  •  V  i^^.^e^n  «"t  off  entirely  for  over  seven  months 
nfZ.  ■  ^  ?™^  ^'"■^'S'}  ^"PPly-  So  severely  have  its  textUe  and 
dee^  Jft""  ^  been  endangered  that  the  British  Govermnent  W 
deemed  it  an  imperative  duty  to  take  the  requisite  steps  to  buiW 
up  promptly  a  national  coal-tar  industry,  depending  upon  nationd 

SranTo^^e^^riyr""^^  "^^  ^"^"""^  ^^^  -*-  --^^"^ 
On  November  27,  1914,  the  President  of  the  British  Board  of  Trade 
m  presentmg  the  subject  before  the  House  of  Commons,  said:  ''If 
we  were  to  go  on  being  dependent  in  the  larger  portion  of  our  textile 
trade  on  suppheswhicTi  Germany  has  the  power'^to  cut  off  whenevS 

Sfn{^'?ri'  T  *'^'  '^f  "»''."?tfJ:  i"  "^  state  Sf  peril,  and  we  sho^d  cer- 
tainly be  lackmg  m  foresight  if  we  were  not  prepared  to  take  the 
steps  nectary  to  put  a  stop  to  the  entire  dependence  of  what  wm 
alter  all   the  greatest  of  our  manufacturing  industries  (i.  e.,  textUe 
manufactures)   on  commodities  entirely  untfer  foreign  controf  " 

hmce  then  the  subiect  has  been  actively  discussed  by  chenjcal  in- 
terests textile  and  cfvers'  associations,  chambers  of  commie  ete 
Some  have  advocated;  a  reversal  of  the  traditional  free-trade  p'oUc^ 
nil  ^g^om.  makmg  a  temporary  exception  in  favor  of  artificial 
dyes,  bome  have  proposed  active  cooperation  with  Switzerland 
whose  dye  production  could  rapidly  be  charged,  raw  matS  S 
suppbed  from  England.  Othe«  favor  ample°fi,iancTal  aid  and  closf 
cooperation  on  the  part  of  the  Govermnent,  with  the  assrance  of 
adequate  protection  agamst  unfair  competition  after  the  war 

1  his  last  pohcy  seems  to  have  the  majority  of  adherents  'and  ha.<? 
received  Government  sanction.  OnFebruary  8  a  definite  plan  was  out^ 
bned  by  theGovemment.  It  is  based  upon  the  formation  of  a  national 
company  with  an  initial  capital  of  $10,000,000.  The  Governmen 
f.ShiiT'^i''  '"'^Tr''^  55,000,000  at  the  rate  of  $1  for  every  $5  sub- 
scribed by  the  pubbc  and  an  additional  $2,500,000  at  the  rate  of  $1 
for  every  $4  subscribed.     Government  advances  receive  4  per  cent 

OTate?v  F»rf  W  !Pr?"^  "^iU  ^'^*'  ^.^"*  $500,000  for  a  research  lab- 
Z^F^  Further  details  with  regard  to  methods  of  protecting  the 
new  mdustry  at  the  close  of  the  war  have  not  yet  been  receivel 

Great  Bntam  uses  annually  about  20,000  tons  of  artificial  dves 
with  an  estimated  value  of  $10,000,000.    The  domestic  manufaS 

Wi^Jf  "t^^'^f^ir  ^'^^  ^"^  ^'^  *°''^'  o'»«-li''W  o^  which  is  exported 
Nme-tenths  of  the  consumption  is  of  German  origin.  "^P^^ea. 


DYESTUFFS  FOB  AMERICAN  INDUSTRIES. 


57 


\ 


< 


i 


fr 


f 


In  France  a  similar  movement  has  been  inaugurated  to  perma- 
nently free  the  country  from  dependence  for  its  dyestuffs  upon 
Germany  or  any  foreign  source.  A  group  of  leading  chemists  has 
devoted  itself  for  some  time  past  to  the  details  of  the  problem. 
Recent  announcements  in  the  press  state  that  it  has  been  satisfac- 
torily solved,  and  that  henceforth  every  phase  of  the  industry  can 
be  established  upon  French  soil,  using  exclusively  French  crude 
materials.  Coal-tar  products  are  supplemented  to  some  extent  by 
residues  from  the  beet-root  sugar  manufacture. 

SUMMARY. 

It   appears   that  numerous  American  industries   are   dependent 
upon  the  use  of  dyestuffs  and  that  artificial  dyestuffs  have  displaced 
nearly;  all  the  natural  dyestuffs;  that  the  American  consumption  of 
artificial  dyestuffs  has  attained  an  annual  value  of  about  $15,000,000 
and  of  this  only  about  $3,000,000  worth  is  supplied  by  domestic 
production,  the  rest  coming  mainly  from  Germany;  that  since  the 
war  in  Europe  German  makers  have  not  been  able  to  supply  the 
entire  demand,  and  in  consequence  prices  have  risen  from  25  to  50 
per  cent  on  such  dyestuffs  as  can  be  dehvered;  that  the  supply  of 
coal-tar  dyestuffs  throughout  the  world  is  completely  dominated 
by  the  German  industry,  Germany  furnishing  in  1913  about  74  per 
cent  of  the  total  world's  consumption;  that  the  German  dyestuff 
mdustry  has   been  chiefly  developed   by  the  inventive  power  of 
German  chemists,  combined  with  a  wealth  of  technical  skill  and  keen 
busings  management  scarcely  equaled  in  the  history  of  any  other 
branch  of  manufacture;  that  in  the  United  States  the  supply  of  coal 
tar  IS  sufficient  to  provide  all  of  the  crudes  required  for  the  manu- 
facture of  the  dyestuffs  consumed  in  the  country;  that  our  manu- 
facture of  heavy  chemicals  is  well  developed  and  able  to  expand 
rapidly  and  supply  all  needed  chemicals  for  the  production  of  inter- 
mediates and  their  transformation  into  finished^  dyes;  that  90  per 
cent  of  the  dyes  now  consumed  in  the  United  States  are  patent-free, 
and  that  the  remainmg  10  per  cent  wUl  soon  be  freed  from  patent 
restriction;  that  the  advance  of  the  American  dyestuff  industry 
beyond  certain  linuts,  is  persistently  checked  and  prevented  by  the 
umted  action  of  German  producers  in  underselUng;  and  that  the 
preseiit  crisis  has  evoked  deep  interest  on  the  part  of  all  concerned— 
tar  distillers,   manufacturers  of  chemicals,   manufacturers  of  dye- 
stuffs,  and  users  of  the  same,  and  economists  in  general— as  to  how 
the  problem  can  be  solved. 

It  appears,  furthermore,  that  some  American  chemical  works  and 
Anierican  manufacturers  of  dyestuffs  are  ready  to  embark  capital 
and  experience  m  very  materially  enlarging  the  present  Umited  scope 
of  the  Amencan  coal-tar  chemical  industry,  usmg  American  crudes 
and  intermediates,  provided  effective  legislation  is  enacted  to  pro- 
Jubit  dumpmg  and  to  prevent  such  action  toward  control  of  our  mar- 
ked by  a  foreign  monopoly  a^  Ls  now  prohibited  to  domestic  industry. 

i^ar-reaching  efforts  *»ppeav  to  have  beeji  made  in  England  and 
i^  ranee  under  Government  auspices  to  free  these  countries  from  de- 
pendence on  any  foreign  .s^rvr'.ce  for  their  supply  of  dyestuffs. 

o  


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COLUMBIA  UNIVERSITY  LIBRARY 

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expiration  of  a  definite  period  after  the  date  oTCowiST 
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rangement  with  the  Librarian  in  char^ 


DATE  BORROWED 


APR  2  a  19 

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